U.S. patent application number 14/951885 was filed with the patent office on 2016-06-02 for self-improving electrocatalysts for gas evolution reactions.
This patent application is currently assigned to William Marsh Rice University. The applicant listed for this patent is Pulickel Ajayan, Ken Hackenberg, Kunttal Keyshar, Yuanyue Liu, Brandon Wood, Jingjie Wu, Boris Yakobson. Invention is credited to Pulickel Ajayan, Ken Hackenberg, Kunttal Keyshar, Yuanyue Liu, Brandon Wood, Jingjie Wu, Boris Yakobson.
Application Number | 20160153098 14/951885 |
Document ID | / |
Family ID | 56078819 |
Filed Date | 2016-06-02 |
United States Patent
Application |
20160153098 |
Kind Code |
A1 |
Hackenberg; Ken ; et
al. |
June 2, 2016 |
SELF-IMPROVING ELECTROCATALYSTS FOR GAS EVOLUTION REACTIONS
Abstract
In some embodiments, the present disclosure pertains to methods
of mediating a gas evolution reaction by exposing a gas precursor
to an electrocatalyst that comprises a plurality of layers with
catalytic sites. The exposing results in electrocatalytic
conversion of the gas precursor to a gas. Thereafter, the generated
gas enhances the electrocatalytic activity of the electrocatalyst
by enhancing the accessibility of the catalytic sites to the gas
precursor. In some embodiments, the electrocatalyst is associated
with an electrically conductive surface (e.g., an electrode) that
provides electrical current. In some embodiments, the
electrocatalyst is a hydrogen production electrocatalyst that
converts H.sup.+ to H.sub.2. In some embodiments, the
electrocatalyst includes a transition metal dichalcogenide. Further
embodiments of the present disclosure pertain to the aforementioned
electrocatalysts for mediating gas evolution reactions.
Inventors: |
Hackenberg; Ken; (Plano,
TX) ; Keyshar; Kunttal; (Tyler, TX) ; Wu;
Jingjie; (Houston, TX) ; Liu; Yuanyue;
(Houston, TX) ; Ajayan; Pulickel; (Houston,
TX) ; Wood; Brandon; (Livermore, CA) ;
Yakobson; Boris; (Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hackenberg; Ken
Keyshar; Kunttal
Wu; Jingjie
Liu; Yuanyue
Ajayan; Pulickel
Wood; Brandon
Yakobson; Boris |
Plano
Tyler
Houston
Houston
Houston
Livermore
Houston |
TX
TX
TX
TX
TX
CA
TX |
US
US
US
US
US
US
US |
|
|
Assignee: |
William Marsh Rice
University
Houston
TX
Lawrence Livermore National Laboratory
Livermore
CA
|
Family ID: |
56078819 |
Appl. No.: |
14/951885 |
Filed: |
November 25, 2015 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62084415 |
Nov 25, 2014 |
|
|
|
Current U.S.
Class: |
205/639 ;
205/637; 205/638; 428/699; 502/216 |
Current CPC
Class: |
Y02E 60/366 20130101;
C25B 11/0478 20130101; C25B 11/04 20130101; Y02E 60/36 20130101;
C25B 1/04 20130101 |
International
Class: |
C25B 11/04 20060101
C25B011/04; C25B 1/04 20060101 C25B001/04 |
Goverment Interests
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
[0002] This invention was made with government support under Grant
No. OISE-0968405, awarded by the National Science Foundation; Grant
No. 12-ERD-053, awarded by the U.S. Department of Energy; and Grant
No. DE-AC52-07NA27344, awarded by the U.S. Department of Energy.
The government has certain rights in the invention.
Claims
1. A method of mediating a gas evolution reaction, wherein the
method comprises: exposing a gas precursor to an electrocatalyst
comprising a plurality of layers, wherein the layers comprise
catalytic sites; wherein the exposing results in electrocatalytic
conversion of the gas precursor to a gas between the layers; and
wherein the gas enhances the electrocatalytic activity of the
electrocatalyst.
2. The method of claim 1, wherein the electrocatalyst is associated
with an electrically conductive surface, wherein the electrically
conductive surface provides electrical current.
3. The method of claim 2, wherein the electrically conductive
surface is an electrode.
4. The method of claim 1, wherein the gas precursor is H.sup.+,
wherein the gas is H.sub.2, and wherein the gas evolution reaction
is a hydrogen evolution reaction that converts H.sup.+ to
H.sub.2.
5. The method of claim 1, wherein the electrocatalyst is a hydrogen
production electrocatalyst that converts H.sup.+ to H.sub.2.
6. The method of claim 1, wherein the electrocatalyst comprises a
transition metal dichalcogenide.
7. The method of claim 6, wherein the transition metal
dichalcogenide comprises a group V transition metal
dichalcogenide.
8. The method of claim 6, wherein the transition metal
dichalcogenide comprises the following formula: MX.sub.2, wherein M
is a transition metal, and wherein X is a chalcogen.
9. The method of claim 8, wherein the transition metal is selected
from the group consisting of Ti, Hf, Zr, Mo, W, Ta, Nb, V, Tc, Re,
Sn and combinations thereof.
10. The method of claim 8, wherein the chalcogen is selected from
the group consisting of S, Se, O, Te, and combinations thereof.
11. The method of claim 8, wherein X is S.
12. The method of claim 1, wherein the electrocatalyst is selected
from the group consisting of TaS.sub.2, NbS.sub.2, VS.sub.2, and
combinations thereof.
13. The method of claim 1, wherein the layers are in the form of
crystal plates.
14. The method of claim 1, wherein the layers are separated by a
distance ranging from about 0.1 nm to about 1 nm.
15. The method of claim 1, wherein the layers are porous.
16. The method of claim 1, wherein the catalytic sites are on
surfaces of the layers.
17. The method of claim 1, wherein the produced gas enhances the
electrocatalytic activity of the electrocatalyst by enhancing the
accessibility of the catalytic sites to the gas precursor.
18. The method of claim 17, wherein the gas enhances the
accessibility of the catalytic sites to the gas precursor by
increasing distances between the layers, thereby making the
catalytic sites more accessible to the gas precursor.
19. The method of claim 17, wherein the produced gas enhances the
electrocatalytic activity of the electrocatalyst with time.
20. The method of claim 1, wherein the electrocatalyst has an
exchange current density ranging from about 2.times.10.sup.-4
A/cm.sup.2 to about 10.times.10.sup.-4 A/cm.sup.2.
21. The method of claim 1, wherein the electrocatalyst has a
catalyst loading that ranges from about 10 .mu.g/cm.sup.2 to about
100 .mu.g/cm.sup.2.
22. The method of claim 1, wherein the electrocatalyst has a Tafel
slope ranging from about of 25 mV/decade to about 100
mV/decade.
23. The method of claim 1, wherein the electrocatalyst has a
current density ranging from about of 5 mA/cm.sup.2 to about 50
mA/cm.sup.2.
24. An electrocatalyst for mediating a gas evolution reaction,
wherein the electrocatalyst comprises a plurality of layers, and
wherein the layers comprise catalytic sites.
25. The electrocatalyst of claim 24, wherein the electrocatalyst is
associated with an electrically conductive surface, wherein the
electrically conductive surface provides electrical current.
26. The electrocatalyst of claim 25, wherein the electrically
conductive surface is an electrode.
27. The electrocatalyst of claim 24, wherein the electrocatalyst is
a hydrogen production electrocatalyst that converts H.sup.+ to
H.sub.2.
28. The electrocatalyst of claim 24, wherein the electrocatalyst
comprises a transition metal dichalcogenide.
29. The electrocatalyst of claim 28, wherein the transition metal
dichalcogenide comprises a group V transition metal
dichalcogenide.
30. The electrocatalyst of claim 28, wherein the transition metal
dichalcogenide comprises the following formula: MX.sub.2, wherein M
is a transition metal, and wherein X is a chalcogen.
31. The electrocatalyst of claim 30, wherein the transition metal
is selected from the group consisting of Ti, Hf, Zr, Mo, W, Ta, Nb,
V, Tc, Re, Sn and combinations thereof.
32. The electrocatalyst of claim 30, wherein the chalcogen is
selected from the group consisting of S, Se, O, Te, and
combinations thereof.
33. The electrocatalyst of claim 30, wherein X is S.
34. The electrocatalyst of claim 24, wherein the electrocatalyst is
selected from the group consisting of TaS.sub.2, NbS.sub.2,
VS.sub.2, and combinations thereof.
35. The electrocatalyst of claim 24, wherein the layers are in the
form of crystal plates.
36. The electrocatalyst of claim 24, wherein the layers are
separated by a distance ranging from about 0.1 nm to about 1
nm.
37. The electrocatalyst of claim 24, wherein the layers are
porous.
38. The electrocatalyst of claim 24, wherein the catalytic sites
are on surfaces of the layers.
39. The electrocatalyst of claim 24, wherein the electrocatalyst
has an exchange current density ranging from about
2.times.10.sup.-4 A/cm.sup.2 to about 10.times.10.sup.-4
A/cm.sup.2.
40. The electrocatalyst of claim 24, wherein the electrocatalyst
has a catalyst loading that ranges from about 10 .mu.g/cm.sup.2 to
about 100 .mu.g/cm.sup.2.
41. The electrocatalyst of claim 24, wherein the electrocatalyst
has a Tafel slope ranging from about of 25 mV/decade to about 100
mV/decade.
42. The electrocatalyst of claim 24, wherein the electrocatalyst
has a current density ranging from about of 5 mA/cm.sup.2 to about
50 mA/cm.sup.2.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 62/084,415, filed on Nov. 25, 2014. The entirety of
the aforementioned application is incorporated herein by
reference.
BACKGROUND
[0003] Current electrocatalysts for mediating gas evolution
reactions have limitations in terms of efficiency, long-term use,
and affordability. The present disclosure addresses these
limitations.
BRIEF SUMMARY
[0004] In some embodiments, the present disclosure pertains to
self-improving methods of mediating a gas evolution reaction. In
some embodiments, the methods include a step of exposing a gas
precursor to an electrocatalyst that includes a plurality of layers
with catalytic sites. In some embodiments, the exposing results in
electrocatalytic conversion of the gas precursor to a gas between
the layers. In some embodiments, the generated gas enhances the
electrocatalytic activity of the electrocatalyst by enhancing the
accessibility of the catalytic sites to the gas precursor. In some
embodiments, the generated gas enhances the accessibility of the
catalytic sites to the gas precursor by increasing distances
between the layers, thereby making the catalytic sites more
accessible to the gas precursor. In some embodiments, the produced
gas enhances the electrocatalytic activity of the electrocatalyst
with time.
[0005] In some embodiments, the electrocatalyst is associated with
an electrically conductive surface that provides electrical
current. In some embodiments, the electrically conductive surface
is an electrode. In some embodiments, the electrocatalyst is a
hydrogen production electrocatalyst that converts H.sup.+ to
H.sub.2.
[0006] In some embodiments, the electrocatalyst includes a
transition metal dichalcogenide. In some embodiments, the
transition metal dichalcogenide includes a group V transition metal
dichalcogenide. In some embodiments, the transition metal
dichalcogenide includes the following formula: MX.sub.2, where M is
a transition metal (e.g., Ti, Hf, Zr, Mo, W, Ta, Nb, V, Tc, Re, Sn
and combinations thereof); and where X is a chalcogen (e.g., S, Se,
O, Te, and combinations thereof). In some embodiments, the
electrocatalyst includes, without limitation, TaS.sub.2, NbS.sub.2,
VS.sub.2, and combinations thereof.
[0007] In some embodiments, the electrocatalyst layers are in the
form of crystal plates. In some embodiments, the electrocatalyst
layers are separated by a distance ranging from about 0.1 nm to
about 1 nm. In some embodiments, the electrocatalyst layers are
porous.
[0008] Further embodiments of the present disclosure pertain to the
aforementioned electrocatalysts for mediating gas evolution
reactions. In some embodiments, the electrocatalysts of the present
disclosure may be associated with fuel cells. In some embodiments,
the methods and electrocatalysts of the present disclosure may be
utilized for generating gases (e.g., hydrogen) directly for fuel
cells within a contained system. In some embodiments, the
electrocatalysts of the present disclosure may be associated with
solar cells. In some embodiments, the methods and electrocatalysts
of the present disclosure may be utilized for generating gases
(e.g., hydrogen) from electricity provided by solar cells.
BRIEF DESCRIPTION OF THE FIGURES
[0009] FIG. 1 provides a scheme of a method of mediating a gas
evolution reaction in accordance with the methods of the present
disclosure.
[0010] FIG. 2 provides data relating to the self-improving
performance of H--TaS.sub.2 catalysts for hydrogen evolution
reactions (HER). FIG. 2A is a schematic illustration of HER at the
surface sites of stacked layers. Spheres represent produced H.sub.2
bubbles formed from H.sup.+. FIGS. 2B-E show atomic force
microscopy (AFM) (FIG. 2B), low-magnification transmission electron
microscopy (TEM) (FIG. 2C), high resolution TEM (HRTEM) (FIG. 2D)
images, and Raman spectra (FIG. 2E) for H--TaS.sub.2 before
cycling, respectively. The inset in FIG. 2B shows the statistical
distribution of thickness for total of 50 platelets. FIGS. 2E-H
show analogous data for the H--TaS.sub.2 after cycling.
[0011] FIG. 3 provides data relating to the physical
characterization of as-grown H--TaS.sub.2 catalysts. FIG. 3A shows
a scanning electron microscopy (SEM) image of the catalysts. FIG.
3B shows a TEM image of the catalyst, showing the layer space of
.about.0.7 nm. FIG. 3C shows Raman spectroscopy of the catalysts.
FIG. 3D shows the x-ray diffraction (XRD) pattern of the catalysts,
showing (001) orientation due to preferred TaS.sub.2 growth on a
SiO.sub.2/Si substrate.
[0012] FIG. 4 shows data relating to the catalytic activity of
H--TaS.sub.2. FIG. 4A shows polarization curves for TaS.sub.2
covered electrodes for various cycling numbers. FIG. 4B shows
current density vs. initial current density with cycling for group
V transition metal dichalcogenides (TMDCs). Current density grows
with cycling to a saturation point and eventually degrades. These
non-optimized samples show the effect of self-nanostructuring.
[0013] FIG. 5 shows a complex impedance plot indicating a sharp
decrease in resistance with cycling as direct evidence for surface
area increase.
[0014] FIG. 6 shows SEM images of H--TaS.sub.2. FIG. 6A shows
H--TaS.sub.2 on electrode before HER. FIG. 6B shows H--TaS.sub.2
after HER with 5000 cycles between 0.2.about.-0.6 V vs. RHE at 5 mV
s.sup.-1. FIGS. 6A-B have different scale bars.
[0015] FIG. 7 shows HRTEM of as-synthesized (FIG. 7A) and
post-cycled (FIG. 7B) H--TaS.sub.2 for 5000 cycles between
0.2.about.-0.6 V vs. RHE at 5 mV s.sup.-1. The post-cycled sample
retains the H hexagonal structure with a cell parameter of a=3.3
.ANG., indicating that the change in sample is not chemical but
purely an increase in available surface area and closer electrical
contact of catalytic sites.
[0016] FIG. 8 provides a states-filling approach based descriptor.
FIG. 8A provides a schematic of MX.sub.2-catalyzed HER. FIG. 8B
provides DOS of pristine and H-adsorbed TiS.sub.2 (coverage of
H:Ti=1:16), with the energy levels with respect to vacuum. The
right inset shows the charge density isosurface for states within
the energy range of Fermi level to -0.025 eV below. FIG. 8C
provides the same information as FIG. 8B but for MoS.sub.2 (M:
blue; X: yellow; H: black; charge density isosurface: red). FIG. 8D
provides a correlation between .epsilon.LUS and the surface
adsorption energy Ea (Eq. 1) of H on a series of MX.sub.2
candidates. TaS.sub.2 (filled circles) are experimentally
synthesized and tested later.
[0017] FIG. 9 provides a prediction of group 5 MX.sub.2 as
surface-active HER catalysts. FIG. 9A provides computed
.epsilon.LUS for all MX.sub.2 candidates, with the target screening
range indicated by dotted lines. Row 4/5/6 elements are shown in
green/red/blue, with the different chalcogens separated into
columns within each group. FIG. 9B provides coverage dependence of
G.sub.tot (from Eq. 2) for H adsorption on the group 5 MX.sub.2.
FIG. 9C provides G.sub.diff (from Eq. 3) for low adsorbate coverage
on the group 5 MX.sub.2 (H:M=1:16), with values for Pt and Ni
surfaces (from (3)) and for active MoS.sub.2 edges shown for
comparison.
[0018] FIG. 10 provides data relating to the electrocatalysis of
HER on TaS.sub.2 and MoS.sub.2. FIG. 10A provides polarization
curves for H--TaS.sub.2, H--MoS.sub.2, T-MoS.sub.2 and T-TaS.sub.2,
measured in 0.5 M H.sub.2SO.sub.4 with a scan rate of 5 mV
s.sup.-1. The H--TaS.sub.2 and H--MoS.sub.2 were first cycled for
5000 cycles between 0.2 and -0.6 V vs. RHE at 100 mV s.sup.-1
before the polarization curve measurement. FIG. 10B shows
corresponding Tafel plots for catalysts in FIG. 10A. The numbers
indicate the Tafel slopes. FIG. 10C shows the exchange current
density obtained by fitting the Tafel plots. FIG. 10D shows the
change of current density (recorded at -0.5 V) during cycling.
[0019] FIG. 11 provides structures of various phases of MX.sub.2.
The red arrow indicates the unit cell.
[0020] FIG. 12 provides diagrams of adsorption energy E.sub.a (Eq.
1) as a function of the charge on the X atom (left) and the d-band
center of bulk M (right).
[0021] FIG. 13 provides data relating to the physical
characterization of as-grown H--TaS.sub.2. An SEM image (FIG. 13A)
and a TEM image (FIG. 13B) show the layer space of .about.0.7 nm. A
Raman spectroscopy (FIG. 13C), and an XRD pattern (FIG. 13D) shows
(001) orientation due to preferred TaS.sub.2 grown on SiO.sub.2/Si
substrate.
[0022] FIG. 14 shows data relating to the physical characterization
of commercial H--MoS.sub.2, including SEM images (FIG. 14A), Raman
spectroscopy (FIG. 14B), and XRD pattern (FIG. 14C).
[0023] FIG. 15 shows data relating to the physical characterization
of T-MoS.sub.2 chemically exfoliated from H--MoS.sub.2, including
SEM images (FIG. 15A), AFM image and corresponding thickness scan
(FIG. 15B), and Raman spectroscopy (FIG. 15C). The T-MoS.sub.2 has
a typical thickness of around 100 nm, which is comparable to the
TaS.sub.2 after 5000 cycles. The emergence of new Raman shifts at
198, 225, and 284 cm.sup.-1 associated with the phonon modes of
T-MoS.sub.2, clearly confirmed the formation of T-MoS.sub.2 from
exfoliation treatment of commercial H--MoS.sub.2 plates.
[0024] FIG. 16 provides data relating to the physical
characterization of exfoliated T-TaS.sub.2, including SEM images
(FIG. 16A), AFM image and corresponding thickness scan (FIG. 16B),
and Raman spectroscopy (FIG. 16C).
[0025] FIG. 17 provides polarization curves recorded during
potential cycling for chemically exfoliated H--MoS.sub.2. The
activity approaches to stability after the first 4 cycles and has
little loss after 1,000 cycles.
[0026] FIG. 18 provides polarization curves of the first three
scans for chemically exfoliated T-TaS.sub.2. The activity was
observed to be decreasing with potential cycling.
[0027] FIG. 19 provides repeated measurement of HER catalytic
activity. Polarization curves of as-synthesized H--TaS.sub.2 and
commercial H--MoS.sub.2 were measured after 3000 cycles between
0.2.about.-0.6 V vs. RHE at a different rate of 5 mV s.sup.-1. The
activity follows the same order as in FIG. 10A.
[0028] FIG. 20 provides the polarization curves recorded
periodically during potential cycling at 5 mV s.sup.-1 for as-grown
H--TaS.sub.2 (FIG. 20A) and commercial H--MoS.sub.2 (FIG. 20B).
[0029] FIG. 21 provides electrochemical impedance spectroscopy
recorded periodically during potential cycling at 5 mV s.sup.-1.
For H--TaS.sub.2 sample, Nyquist plots show the decreasing of
charge transfer resistance with cycling (FIGS. 21A-B). FIG. 21C
shows Bode plots demonstrating frequency response. FIGS. 21D-F show
data analogous to FIGS. 21A-C for H--MoS.sub.2.
[0030] FIG. 22 shows SEM images of bulk H--TaS.sub.2 after 5000
cycling between 0.2.about.-0.6 V vs. RHE at 5 mV s.sup.-1. FIG. 22A
shows low-magnification image of H--TaS.sub.2 crystals on electrode
before HER. FIG. 22B shows high-magnification image of smaller and
thinner H--TaS.sub.2 after HER.
[0031] FIG. 23 shows HRTEM of as-synthesized (FIG. 23A) and
post-cycled H--TaS.sub.2 (FIG. 23B) for 5000 cycles between
0.2.about.-0.6 V vs. RHE at 5 mV s.sup.-1. The post-cycled sample
remains the H hexagonal structure with the cell parameter a=3.3
.ANG..
[0032] FIG. 24 shows a comparison between fresh H--MoS.sub.2 and
post-cycled H--MoS.sub.2 for 5000 cycles between 0.2.about.-0.6 V
vs. RHE at 5 mV s.sup.-1. FIGS. 24A-B show SEM and TEM of the fresh
H--MoS.sub.2 transferred on the GC electrodes, respectively. FIGS.
24C-D are analogous to FIGS. 24A-B for post-cycled H--MoS.sub.2. No
dramatic thinning of thickness and breaking of size was observed
for H--MoS.sub.2 after cycling. No pore on the surface was seen
either.
DETAILED DESCRIPTION
[0033] It is to be understood that both the foregoing general
description and the following detailed description are illustrative
and explanatory, and are not restrictive of the subject matter, as
claimed. In this application, the use of the singular includes the
plural, the word "a" or "an" means "at least one", and the use of
"or" means "and/or", unless specifically stated otherwise.
Furthermore, the use of the term "including", as well as other
forms, such as "includes" and "included", is not limiting. Also,
terms such as "element" or "component" encompass both elements or
components comprising one unit and elements or components that
comprise more than one unit unless specifically stated
otherwise.
[0034] The section headings used herein are for organizational
purposes and are not to be construed as limiting the subject matter
described. All documents, or portions of documents, cited in this
application, including, but not limited to, patents, patent
applications, articles, books, and treatises, are hereby expressly
incorporated herein by reference in their entirety for any purpose.
In the event that one or more of the incorporated literature and
similar materials defines a term in a manner that contradicts the
definition of that term in this application, this application
controls.
[0035] The generation of gases finds applications in many fields.
For instance, hydrogen is an ideal energy carrier and an important
agent for many industrial chemical processes. One popular method
for generating hydrogen sustainably is electrolysis via the
hydrogen evolution reaction (HER), in which aqueous protons are
electrochemically reduced with the aid of an appropriate
catalyst--traditionally, an expensive noble-metal.
[0036] Recently, layered molybdenum (Mo) and tungsten (W)
transition-metal dichalcogenides (MX.sub.2) have attracted
substantial interest as earth-abundant, inexpensive replacements
for precious-metal HER catalysts. Unfortunately, their performance
is limited by the low density of catalytically active sites, which
are mainly located at the edges. [T. Jaramillo et al., Science Vol.
317 no. 5834 pp. 100-102 (2007)]. As such, a need exists for more
effective electrocatalysts to mediate various gas evolution
reactions, including HER.
[0037] In some embodiments, the present disclosure provides
self-improving methods of mediating gas evolution reactions. In
some embodiments that are illustrated in FIG. 1, the methods of the
present disclosure include a step of exposing a gas precursor to an
electrocatalyst (step 10). In some embodiments, the exposing
results in electrocatalytic conversion of the gas precursor to a
gas (step 12). In some embodiments, the generated gas enhances the
electrocatalytic activity of the electrocatalyst (step 14).
Thereafter, the electrocatalyst may be utilized to mediate
additional electrocatalytic reactions. Additional embodiments of
the present disclosure pertain to the self-improving
electrocatalysts for mediating gas evolution reactions.
[0038] As set forth in more detail herein, the methods of the
present disclosure may utilize various types of electrocatalysts.
Various methods may also be utilized to expose the electrocatalysts
of the present disclosure to various gas precursors to result in
the generation of various gases. Moreover, the generated gases may
enhance the electrocatalytic activity of the electrocatalysts of
the present disclosure by various mechanisms.
[0039] Electrocatalysts
[0040] The electrocatalysts of the present disclosure generally
include a plurality of layers. In some embodiments, the layers
include catalytic sites for mediating gas evolution reactions.
[0041] The electrocatalysts of the present disclosure can have
various compositions. In some embodiments, the electrocatalysts of
the present disclosure exclude noble metals, such as Pt and Pd. In
some embodiments, the electrocatalysts of the present disclosure
exclude Pt and Pd. In some embodiments, the electrocatalysts of the
present disclosure include transition metal dichalcogenides. In
some embodiments, the transition metal dichalcogenides of the
electrocatalysts of the present disclosure include group V
transition metal dichalcogenides. In some embodiments, the
transition metal dichalcogenides of the electrocatalysts of the
present disclosure include group V transition metal disulfides. In
some embodiments, the electrocatalysts of the present disclosure
include, without limitation, TaS.sub.2, NbS.sub.2, VS.sub.2, and
combinations thereof. In some embodiments, the electrocatalysts of
the present disclosure include TaS.sub.2.
[0042] In some embodiments, the electrocatalysts of the present
disclosure include transition metal dichalcogenides with the
following formula:
MX.sub.2.
[0043] In the above formula, M is a transition metal and X is a
chalcogen. In some embodiments, M includes, without limitation, Ti,
Hf, Zr, Mo, W, Ta, Nb, V, Tc, Re, Sn, and combinations thereof. In
some embodiments, M excludes noble metals, such as at least one of
Pt and Pd. In some embodiments, M excludes Pt and Pd. In some
embodiments, X includes, without limitation, S, Se, O, Te, and
combinations thereof. In some embodiments, X is S.
[0044] In some embodiments, the transition metal dichalcogenides
are in the H phase. In some embodiments, the transition metal
dichalcogenides are in the T phase. In some embodiments, the
transition metal dichalcogenides are in the H phase and the T
phase.
[0045] The electrocatalysts of the present disclosure may have
various types of layers. In some embodiments, the layers are in the
form of plates, such as crystal plates. In some embodiments, the
layers are porous. In some embodiments, the layers are in the form
of porous membranes. In some embodiments, the layers are dispersed
within a proton exchange membrane, such as Nafion. In some
embodiments, the layers are associated with one another through van
der Waals interactions. In some embodiments, the layers are
stacked.
[0046] In some embodiments, catalytic sites are located on the
surfaces of the layers. In some embodiments, catalytic sites are
located on the edges of the layers. In some embodiments, the
catalytic sites are located on the surfaces and edges of the
layers. In some embodiments, the catalytic sites are uniformly
dispersed throughout the surfaces of the layers. In some
embodiments, the catalytic sites have the same compositions as the
electrocatalysts of the present disclosure. In some embodiments,
the location of the catalytic sites causes the self-optimizing
performance.
[0047] In some embodiments, the layers (e.g., stacks of layers)
have thicknesses ranging from about 50 nm to about 1000 nm. In some
embodiments, the layers (e.g., stacks of layers) have thicknesses
ranging from about 100 nm to about 600 nm. In some embodiments, the
layers are separated by a distance ranging from about 0.1 nm to
about 1 nm. In some embodiments, the layers are separated by a
distance of about 0.7 nm. In some embodiments, the layers have
surface areas that range from about 0.1 nm.sup.2 to about 1
m.sup.2.
[0048] In some embodiments, the layers (e.g., stacks of layers)
have widths ranging from about 1 .mu.m to about 10 mm. In some
embodiments, the layers (e.g., stacks of layers) have widths
ranging from about 1 .mu.m to about 100 .mu.m. In some embodiments,
the layers have widths ranging from about 1 .mu.m to about 50
.mu.m. In some embodiments, the layers have widths ranging from
about 1 .mu.m to about 20 .mu.m. In some embodiments, the layers
have widths ranging from about 1 .mu.m to about 10 .mu.m.
[0049] The electrocatalysts of the present disclosure may also be
associated with various surfaces. For instance, in some
embodiments, the electrocatalysts of the present disclosure are
associated with an electrically conductive surface. In some
embodiments, the electrically conductive surface provides
electrical current that mediates the gas evolution reaction.
[0050] In some embodiments, the electrically conductive surface is
an electrode. In some embodiments, the electrically conductive
surface is a cathodic electrode (e.g., glassy carbon). In some
embodiments, the electrically conductive surface is an anodic
electrode.
[0051] Gas Evolution Reactions
[0052] The methods and electrocatalysts of the present disclosure
may be utilized to mediate various types of electrocatalytic
reactions. Gas evolution reactions are mediated by exposing a gas
precursor to an electrocatalyst. In some embodiments, the gas
precursor is a proton (i.e., H.sup.+), such as an aqueous
proton.
[0053] In some embodiments, the electrocatalysts of the present
disclosure are hydrogen production electrocatalysts that mediate
hydrogen evolution reactions (e.g., conversion of H.sup.+ to
H.sub.2). In such embodiments, the gas precursor is H.sup.+, and
the generated gas is H.sub.2. In some embodiments, the hydrogen
evolution reaction can be mediated in accordance with the following
formula:
2H.sup.++2e.sup.-.fwdarw.H.sub.2
[0054] Enhancement of Electrocatalytic Activity
[0055] The methods of the present disclosure may enhance the
electrocatalytic activity of electrocatalysts by various
mechanisms. For instance, in some embodiments, the produced gas
from a gas evolution reaction enhances the electrocatalytic
activity of the electrocatalyst by enhancing the accessibility of
the catalytic sites to the gas precursor. In some embodiments, the
gas enhances the accessibility of the catalytic sites to the gas
precursor by increasing distances between the electrocatalyst
layers, thereby making the catalytic sites more accessible to the
gas precursor. In some embodiments, gas generation causes
separation of layers, thereby increasing the effective surface area
of the electrocatalyst.
[0056] In some embodiments, gas generation results in a mechanical
self-structuring (e.g., self-nanostructuring) of the
electrocatalyst, which in turn leads to the enhancement of the
electrocatalyst's electrocatalytic activity. In some embodiments,
the mechanical self-structuring includes the optimization of the
electrocatalyst morphology for mediating gas evolution reactions.
In some embodiments, the optimization of the morphology results in
enhanced basal-plane electrocatalytic activity within
electrocatalyst layers. In some embodiments, the optimization of
the morphology results in enhanced charge transfer between the
layers (e.g., by shortening the electron-transfer pathways between
the layers). In some embodiments, the optimization of the
morphology results in an increase in the accessibility of the
catalytic sites to the gas precursor.
[0057] In some embodiments, the produced gas enhances the
electrocatalytic activity of the electrocatalyst with time. In some
embodiments, the electrocatalytic activity of the electrocatalyst
increases with use. In some embodiments, fresh unused catalytic
sites are made accessible over time. In some embodiments, an
increase in available catalytic sites improves the activity of the
electrocatalysts and prolongs the life of the electrocatalyst
itself. In some embodiments, electrocatalytic activity of the
electrocatalysts increases over tens of thousands of cycles of
use.
[0058] In some embodiments, the electrocatalysts of the present
disclosure have an exchange current density ranging from about
2.times.10.sup.-4 A/cm.sup.2 to about 10.times.10.sup.-4
A/cm.sup.2. In some embodiments, the electrocatalysts of the
present disclosure have a catalyst loading that ranges from about
10 .mu.g/cm.sup.2 to about 100 .mu.g/cm.sup.2. In some embodiments,
the electrocatalysts of the present disclosure have a Tafel slope
ranging from about of 25 mV/decade to about 100 mV/decade. In some
embodiments, the electrocatalysts of the present disclosure have a
current density ranging from about 5 mA/cm.sup.2 to about 50
mA/cm.sup.2.
[0059] Applications and Advantages
[0060] The methods and electrocatalysts of the present disclosure
provide a first demonstration where an electrocatalyst enhances its
electrocatalytic performance with use (i.e., self-improvement) to
form complex nanostructures with high surface areas. Moreover, the
electrocatalysts of the present disclosure can be fabricated from
affordable materials in bulk quantities.
[0061] As such, the methods and electrocatalysts of the present
disclosure could be used as low cost alternatives for producing
various types of gases (including hydrogen by HER) without the use
of rare or expensive catalysts, such as platinum and nanostructured
MoS.sub.2.
[0062] Moreover, the methods and electrocatalysts of the present
disclosure may be utilized for various applications, including use
in energy storage devices and energy conversion devices. In some
embodiments, the methods and electrocatalysts of the present
disclosure may be utilized for generating gases (e.g., hydrogen)
directly for fuel cells within a contained system. In some
embodiments, the methods and electrocatalysts of the present
disclosure may be utilized for generating gases (e.g., hydrogen)
from electricity provided by solar cells.
[0063] Accordingly, the electrocatalysts of the present disclosure
may be associated with various types of energy storage and energy
conversion devices. In some embodiments, the electrocatalysts of
the present disclosure may be associated with fuel cells. In some
embodiments, the electrocatalysts of the present disclosure may be
associated with solar cells.
Additional Embodiments
[0064] Reference will now be made to more specific embodiments of
the present disclosure and experimental results that provide
support for such embodiments. However, Applicants note that the
disclosure below is for illustrative purposes only and is not
intended to limit the scope of the claimed subject matter in any
way.
Example 1
Self-Nanostructuring and Self-Improving Catalysts for Hydrogen
Evolution Reactions
[0065] In this Example, Applicants provide a device and its
application in which surface catalytic activity on layers within a
material causes self-nanostructuring of the catalyst during use for
increase in effective surface area. This Example focuses on the use
of Group V transition metal dichalcogenides as catalysts. However,
this effect is expected for any layered material that is surface
catalytic for gas (e.g., H.sub.2) production.
[0066] As illustrated in FIG. 2A, a new class of hydrogen
production catalysts is described in this Example, where mechanical
self-nanostructuring is forced by the expansion of hydrogen gas
produced. Since the hydrogen gas is produced locally at active
sites, which include basal surface sites of 2H-TaS.sub.2 (and Group
V TMDCs in general) within the material, pressure is created
between layers. Thereafter, it is envisioned that the
surface-activity-caused nanostructuring of 2H-TaS.sub.2 platelets
increases the electron transfer (FIG. 5) and improves accessibility
of basal surface sites, contributing to the observed increase in
catalytic activity.
Example 1.1
CVD Synthesis Method
[0067] NbS.sub.2 and TaS.sub.2 crystal platelets are grown by a
chemical vapor deposition on SiO.sub.2/Si substrates from sulfur
and tantalum chloride powders and gaseous hydrogen precursors in a
3-stage furnace via the following reactions where M=Nb or Ta:
H 2 + ( 1 8 ) S 8 .fwdarw. H 2 S ##EQU00001## M Cl 5 + H 2 S + ( 1
2 ) H 2 .fwdarw. M S 2 + ( 5 ) H Cl ##EQU00001.2##
[0068] In one growth example, sulfur, transition metal chloride,
and growth substrate regions are held respectively at
.about.250.degree. C., .about.300.degree. C., and
.about.750.degree. C. for a 10 minute growth period with a 20 sccm
flow of Ar/H.sub.2 (85:15). Different temperatures yield different
crystal phases which can have varying catalytic activity. VS.sub.2
platelets are similarly grown from VO.sub.x precursors in a sulfur
atmosphere.
Example 1.2
Direct Synthesis Method
[0069] Stoichiometric quantities of pure metal and sulfur are
sealed in evacuated and Argon backfilled quartz tubes, heated to
and held at 750-1000 degrees and cooled depending on a desired
phase.
Example 1.3
Hydrogen Evolution Reaction (HER) Setup
[0070] Powders and plates are inherently catalytic for HER, but
should preferably be in electrical contact with an electrode in the
hydrogen production setup. However, other methods in which a
catalyst is in contact with an electrode can also be utilized.
Example 1.4
Electrochemical Studies
[0071] Electrochemical measurements were performed in a
three-electrode electrochemical cell using a Autolab PGSTAT302N
potentiostat. All measurements were performed in 50 mL of 0.5 M
H.sub.2SO.sub.4 (aq) electrolyte (pH=0.16) prepared using 18
M.OMEGA. deionized water purged with Ar gas (99.999%). The glassy
carbon electrode (CH Instruments, Dia. 3 mm) casted by the samples
was employed as the working electrode while a graphite rod and a
saturated calomel electrode (SCE) (CH Instruments) was used as a
counter and a reference electrode, respectively. A glassy carbon
plate loaded with H--TaS.sub.2 samples was also employed as a
working electrode in order to monitor the morphology change during
long-time potential cycling.
[0072] The reversible hydrogen electrode (RHE) was calibrated in
the high purity H.sub.2 saturated electrolyte using platinum as
both working and counter electrodes. Cyclic voltammetry (CVs) was
run at a scan rate of 1 mV s.sup.-1, and the average of the two
potentials at which the current crossed zero was taken to be the
thermodynamic potential for the hydrogen electrode reactions. In
0.5 M H.sub.2SO.sub.4, E (RHE)=E (SCE)+0.254 V.
[0073] The hydrogen evolution reaction (HER) was measured using
linear sweep voltammetry between +0.10.about.-0.50 V vs. RHE with a
scan rate of 5 mV s.sup.-1. The stability was evaluated by the
potential cycling performed using CVs initiating at +0.2 V and
ending at -0.6 V vs. RHE at either 100 mV s.sup.-1 or 5 mVs.sup.-1.
All data are corrected for a small ohmic drop using electrochemical
impedance spectroscopy (EIS). EIS was performed at a biased
potential of -0.4 V vs. RHE while sweeping the frequency from 1 MHz
to 10 mHz with a 5 mV AC amplitude. The catalytic performance
curves have been iR corrected in the measurements.
Example 1.5
Electrode Preparation
[0074] Electrodes were prepared by a mechanical transfer technique.
A Bic rubber eraser was lightly rubbed against the sample is one
directional strokes and then the eraser was gently tapped against
the glassy carbon electrode. The electrode is weighed before and
after in order to calculate the loading density. The loading
density of all catalyst materials compared was 15
.mu.m/cm.sup.2.
Example 1.6
Characterizations
[0075] Scanning electron microscopy (SEM) images were recorded on
an FEI Quanta 400 microscope. Atomic force microscopy (AFM)
measurements were taken using an Agilent Picoscan 5500 AFM equipped
with a silicon tapping mode tip (AppNano). In the case of comparing
the morphology before and after potential cycling, SEM and AFM
images were taken on the samples loaded onto the glassy carbon
plate. Transmission electron microscopy (TEM) images were collected
on a JEOL 2100F TEM. Samples were prepared by drop-drying a diluted
suspension in isoproponal onto copper grids covered with lacy
carbon films. X-ray diffraction (XRD) was carried out on a Rigaku
D/Max Ultima II Powder XRD. Raman spectra were carried out at an
excitation wave length of 514 nm.
Example 1.7
Catalyst Performance
[0076] Applicants measured an increase in current with use due an
increase in number of available catalytic sites as a result of
separation of atomic layers during hydrogen production. An
additional implication is that newly exposed catalytic sites have
high activity, providing a continuous source of new catalysts. This
is in stark contrast to other catalysts where performance decreases
with use as number of active sites is fixed and individual sites
degrade in efficacy over time (Table 1).
TABLE-US-00001 TABLE 1 Comparison of hydrogen evolution reaction
(HER) activities of previously reported catalysts and the catalysts
in this Example. Catalyst loading j.sub.0 Tafel slope j@-0.15 V vs.
Sample (.mu.g/cm.sup.2) (A/cm.sup.2) (mV/decade) RHE (mA/cm.sup.2)
Ref Nanoparticulate MoS.sub.2 N/A 1.3-3.7 .times. 10.sup.-7 55-60
0.2 (12) Particulate MoS.sub.2 4 4.6 .times. 10.sup.-6 120 0.5 (13)
Double gyroid MoS.sub.2 60 6.9 .times. 10.sup.-7 50 1 (14) Edge
exposed MoS.sub.2 film 8.5 2.2 .times. 10.sup.-6 105-120 0.06 (15)
Edge exposed MoS.sub.2 film 22 1.71-3.40 .times. 10.sup.-6 115-123
0.1 (16) 30 nm MoS.sub.2 3400-3900 5.0 .times. 10.sup.-5 66 10.3
(17) T- MoS.sub.2 50 N/A 40 1 (18) T- MoS.sub.2 N/A N/A 43 2 (19)
MoS.sub.2/RGO 285 5.1 .times. 10.sup.-6 41 8 (20) Defect-Rich
MoS.sub.2 285 8.9 .times. 10.sup.-6 50 3 (21) Electrodeposited
MoS.sub.2 N/A N/A 106 2 (22) MoS.sub.2/CNT-graphene 650 2.91
.times. 10.sup.-5 100 2 (23) NanoflakesWS.sub.2 350 N/A 48 1 (24)
WS.sub.2/RGO 400 N/A 58 2 (25) T-WS.sub.2 6.5 .sup. 1 .times.
10.sup.-6 60 1 (26) H-TaS.sub.2 50 9.2 .times. 10.sup.-4 99 19 Self
nanostructuring catalyst
REFERENCES
[0077] 1. P. E. Blochl, Projector augmented-wave method. Phys. Rev.
B 50, 17953 (1994). [0078] 2. G. Kresse, D. Joubert, From ultrasoft
pseudopotentials to the projector augmented-wave method. Phys. Rev.
B 59, 1758 (1999). [0079] 3. J. P. Perdew, K. Burke, M. Ernzerhof,
Generalized Gradient Approximation Made Simple. Phys. Rev. Lett.
77, 3865 (1996). [0080] 4. G. Kresse, J. Furthmuller, Efficient
iterative schemes for ab initio total-energy calculations using a
plane-wave basis set. Phys. Rev. B 54, 11169 (1996). [0081] 5. G.
Kresse, J. Hafner, Ab initio molecular dynamics for liquid metals.
Phys. Rev. B 47, 558 (1993). [0082] 6. H. J. Monkhorst, J. D. Pack,
Special points for Brillouin-zone integrations. Phys. Rev. B 13,
5188 (1976). [0083] 7. B. Hinnemann et al., Biomimetic Hydrogen
Evolution: MoS2 Nanoparticles as Catalyst for Hydrogen Evolution.
J. Am. Chem. Soc. 127, 5308 (2005 Apr. 1, 2005). [0084] 8. K.
Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, R. G.
Hennig, Implicit solvation model for density-functional study of
nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140,
(2014). [0085] 9. S. A. Petrosyan, A. A. Rigos, T. A. Arias, Joint
Density-Functional Theory: Ab Initio Study of Cr2O3 Surface
Chemistry in Solution. J. Phys. Chem. B 109, 15436 (2005 Aug. 1,
2005). [0086] 10. M. S. Faber, S. Jin, Earth-abundant inorganic
electrocatalysts and their nanostructures for energy conversion
applications. Energy Environ. Sci., (2014). [0087] 11. B. Hammer,
J. K. Norskov, in Advances in Catalysis, H. K. Bruce C. Gates, Ed.
(Academic Press, 2000), vol. Volume 45, pp. 71-129. [0088] 12. T.
F. Jaramillo et al., Identification of Active Edge Sites for
Electrochemical H2 Evolution from MoS2 Nanocatalysts. Science 317,
100 (Jul. 6, 2007, 2007). [0089] 13. J. Bonde, P. G. Moses, T. F.
Jaramillo, J. K. Norskov, I. Chorkendorff, Hydrogen evolution on
nano-particulate transition metal sulfides. Faraday Discussions
140, 219 (2009). [0090] 14. J. Kibsgaard, Z. Chen, B. N. Reinecke,
T. F. Jaramillo, Engineering the surface structure of MoS2 to
preferentially expose active edge sites for electrocatalysis.
Nature Mate. 11, 963 (November, 2012). [0091] 15. D. Kong et al.,
Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers.
Nano Lett. 13, 1341 (2013 Mar. 13, 2013). [0092] 16. H. T. Wang et
al., Electrochemical tuning of vertically aligned MoS2 nanofilms
and its application in improving hydrogen evolution reaction.
Proceedings of the National Academy of Sciences of the United
States of America 110, 19701 (December, 2013). [0093] 17. H. Wang
et al., Electrochemical Tuning of MoS2 Nanoparticles on
Three-Dimensional Substrate for Efficient Hydrogen Evolution. ACS
Nano 8, 4940 (2014 May 27, 2014). [0094] 18. D. Voiry et al.,
Conducting MoS2 Nanosheets as Catalysts for Hydrogen Evolution
Reaction. Nano Lett. 13, 6222 (2013 Dec. 11, 2013). [0095] 19. M.
A. Lukowski et al., Enhanced Hydrogen Evolution Catalysis from
Chemically Exfoliated Metallic MoS2 Nanosheets. J. Am. Chem. Soc.
135, 10274 (2013 Jul. 17, 2013). [0096] 20. Y. Li et al., MoS2
Nanoparticles Grown on Graphene: An Advanced Catalyst for the
Hydrogen Evolution Reaction. J. Am. Chem. Soc. 133, 7296 (May 18,
2011). [0097] 21. J. Xie et al., Defect-Rich MoS2 Ultrathin
Nanosheets with Additional Active Edge Sites for Enhanced
Electrocatalytic Hydrogen Evolution. Advanced Materials 25, 5807
(2013). [0098] 22. S. Murugesan et al., Room Temperature
Electrodeposition of Molybdenum Sulfide for Catalytic and
Photoluminescence Applications. ACS Nano 7, 8199 (2013 Sep. 24,
2013). [0099] 23. D. H. Youn et al., Highly Active and Stable
Hydrogen Evolution Electrocatalysts Based on Molybdenum Compounds
on Carbon Nanotube-Graphene Hybrid Support. ACS Nano 8, 5164 (2014
May 27, 2014). [0100] 24. L. Cheng et al., Ultrathin WS2 Nanoflakes
as a High-Performance Electrocatalyst for the Hydrogen Evolution
Reaction. Angewandte Chemie International Edition, n/a (2014).
[0101] 25. J. Yang et al., Two-Dimensional Hybrid Nanosheets of
Tungsten Disulfide and Reduced Graphene Oxide as Catalysts for
Enhanced Hydrogen Evolution. Angewandte Chemie International
Edition 52, 13751 (2013). [0102] 26. D. Voiry et al., Enhanced
catalytic activity in strained chemically exfoliated WS2 nanosheets
for hydrogen evolution. Nature Mate. 12, 850 (September, 2013).
Example 2
Surface-Active Metal Dichalcogenide Electrocatalysts with
Self-Improving Performance for Hydrogen Evolution
[0103] Efficient electrochemical production of hydrogen (H.sub.2)
without the use of expensive precious-metal catalysts has attracted
intense interest. Layered transition-metal dichalcogenides
(MX.sub.2) based on molybdenum and tungsten are promising
catalysts. However, their performance is limited by the
availability of active catalytic sites, located mainly at the
edges. With the aim of finding higher-performance surface-active
MX.sub.2 catalysts, Applicants apply first-principles methods in
this Example to reveal simple underlying factors in the electronic
structure that ultimately determine catalytic performance. Using
these factors as a descriptor for catalyst screening, Applicants
predict particularly high intrinsic surface-site activity for group
5 transition metal sulfides (VS.sub.2, NbS.sub.2, TaS.sub.2). This
prediction is directly verified experimentally by tests on
TaS.sub.2, whose high surface activity leads to overall performance
exceeding that of the best edge-active MX.sub.2 competitors.
Moreover, the performance of TaS.sub.2 improves upon cycling, as a
result of its surface activity. In this Example, Applicants
illustrate how theory-motivated rational design guidelines can be
formulated and applied for materials screening and discovery.
[0104] In this Example, Applicants use first-principles
calculations to unravel the underlying electronic factors that
correlate with surface catalytic activity on MX.sub.2. Such
insights directly lead to the prediction and experimental
demonstration of extraordinary HER activity for group 5 metal
sulfides.
[0105] The HER proceeds via two steps, as illustrated in FIG. 8A:
(i) H first adsorbs on the catalyst by
H.sup.++e.sup.-+*.fwdarw.H*(Volmer reaction), where * denotes a
catalytic site; (ii) then an H.sub.2 molecule is formed and
desorbed by either 2H*.fwdarw.H.sub.2+2*(Tafel reaction) or
H.sup.++e.sup.-+H*.fwdarw.H.sub.2+*(Heyrovsky reaction). An ideal
catalyst should provide an optimal balance between adsorption and
desorption--a behavior known as the Sabatier principle, typified by
the "volcano plot". If the substrate interaction is too weak, then
the Volmer reaction is inhibited; if it is too strong, then the
Tafel/Heyrovksy reaction cannot proceed. The relative adsorption
free energy of the H* intermediate therefore acts as an indicator
of the catalytic activity.
[0106] Computing the adsorption free energy on all possible
MX.sub.2 combinations depends on the loading density and must be
done even for dilute concentrations, which require large unit
cells. Instead, Applicants searched for a descriptor based on the
intrinsic substrate electronic structure that can readily predict
adsorption without the need for explicit calculation, permitting
rapid primary screening of MX.sub.2 catalysts. To test possible
descriptors, Applicants initially target successful prediction of
the dilute H adsorption energy, which Applicants assume captures
the dominant contributions to the adsorption free energy.
Applicants define this adsorption energy in accordance with the
following formula:
Ea=E(H+MX.sub.2)-E(MX.sub.2)-E(H.sub.2)/2.
[0107] In the above formula, E(H+MX.sub.2), E(MX.sub.2) and
E(H.sub.2) are the energy of H-adsorbed MX.sub.2, pure MX.sub.2,
and an H.sub.2 molecule, respectively. All quantities are
calculated using density functional theory (DFT).
[0108] Although binding-energy descriptors based on the metal
d-band center have demonstrated success for transition-metal
systems (17-19), they cannot be applied to surface binding on
MX.sub.2, given that H attaches to the X atom rather than the M
atom (FIG. 12). The interaction may be dominated by local
electrostatics, in which case the charge on X at the adsorption
site might be an appropriate descriptor. However, no such
correlation was observed (FIG. 12). Instead, a new descriptor was
utilized.
[0109] To design a proper descriptor with broad applicability,
Applicants first examine changes in the underlying electronic
structure of two representative MX.sub.2 materials, metallic
(TiS.sub.2) and semiconducting (MoS.sub.2), upon adsorption.
Applicants use a single adsorbate in a 4.times.4 unit cell to
approximate dilute adsorption. For metallic TiS.sub.2 (FIG. 8B), H
adsorption does not change the overall profile of the electronic
density of states (DOS), but rather shifts the Fermi level
(.epsilon.F) to a slightly higher energy (i.e., occupies previously
empty states). This shift in .epsilon.F corresponds to 1e per H
adsorbate, indicating complete charge transfer to TiS.sub.2. The
charge density distribution shows that the transferred electrons
are delocalized throughout the M layer. For semiconducting
MoS.sub.2 (FIG. 8C), the DOS profile also remains largely intact,
with the exception of a new narrow band immediately below the
conduction band minimum (.epsilon.CBM) that is occupied by the
transferred electrons. In other words, H behaves like a shallow
n-type dopant. The charge density distribution shows that this
state is quasi-localized in space. Applicants can extrapolate the
behavior of both materials to the dilute adsorption limit, where
the number of transferred electrons becomes negligible with respect
to the total DOS. In this case, the Fermi level of the metallic
system (TiS.sub.2) would remain unchanged by adsorption, whereas
the Fermi level of the semiconducting system (MoS.sub.2) would
shift to the newly created localized state, which is pinned close
to .epsilon.CBM. In addition, the DOS profile of each would be
retained.
[0110] Notably, this behavior is consistent with a model based on
the `states-filling work`, which was recently proposed as an
appropriate descriptor for predicting charge-transfer binding on
sp.sup.2-carbon substrates (20). It is based on a rigid-band
approximation, which assumes the underlying substrate DOS profile
is unaffected by the adsorbate. Moreover, when operating at the
dilute adsorption limit, the states-filling work converges to the
energy of the lowest unoccupied state (LUS) .epsilon.LUS, equal to
.epsilon.F for metals or .epsilon.CBM for semiconductors (20),
which agrees well with the two representative cases in the dilute
limit.
[0111] The suitability of .epsilon.LUS as a descriptor is confirmed
in FIG. 8D. Applicants calculate this quantity for a set of known
MX.sub.2 species (based on the substrate alone without an
adsorbate) and compare the result to the dilute H adsorption
energy, evaluated explicitly using Eq. 1. The two values correlate
linearly with a slope of near unity (FIG. 8D). This implies that
differences in Ea amongst the various substrates originate almost
exclusively from differences in .epsilon.LUS, and that the key to
adjusting the H adsorption energy lies in the vacuum-referenced
placement of the substrate LUS level.
[0112] Having established .epsilon.LUS as a viable descriptor for
Ea on MX.sub.2 surfaces, Applicants proceed to select its target
value that will give a reasonable range of surface adsorption
strengths for primary catalyst screening. A target estimate for
.epsilon.LUS is obtained by examining results for the H phases of
MoX.sub.2 and WX.sub.2. According to FIG. 8D, these surfaces have a
comparatively high .epsilon.LUS (>-4.5 eV), which leads to weak
surface adsorption (Ea>2.0 eV/H). This prevents the Volmer
reaction from taking place and inhibits surface activity (3, 4). In
contrast, the active edges of these materials have much stronger Ea
(calculated as .about.-0.4 eV/H for MoS.sub.2 edge (see Examples
2.1-2.5), which is apparently more appropriate for effective
catalysis. Substituting Ea=-0.4 eV/H into the linear trend in FIG.
8D, Applicants conclude that materials with .epsilon.LUS.about.-6.3
eV would have adsorption strengths competitive with MoX.sub.2 and
WX.sub.2 edges. Applicants broaden this criterion for viable
candidates to -0.5 eV/H<Ea<+0.5 eV/H, corresponding to -6.4
eV<.epsilon.LUS<-5.5 eV. As additional validation, Applicants
point out the T' phases of MoS.sub.2 and WS.sub.2 have values of
.epsilon.LUS within this range (-5.7 and -5.6 eV, respectively),
and each has recently demonstrated correspondingly enhanced HER
activity with respect to the ordinary H phases.
[0113] Applying the .epsilon.LUS criterion to all MX.sub.2
substrates in their most stable phases (H for group 5 and 6, T for
group 4 and 10, T' for group 7; structures described in Examples
2.1-2.5), Applicants narrow the list of viable surface-active HER
catalysts to a small handful of candidates (FIG. 9A). Two general
features are observed. (1) For a given M, .epsilon.LUS increases in
the following order: S<Se<Te. Hence, Ea increases in the
following order: S<Se<Te. (2) Metallic MX.sub.2 candidates
(from groups 4 and 5) have lower .epsilon.LUS and hence stronger Ea
than semiconducting MX.sub.2 candidates (from groups 6, 7, and 10).
The group 5 metal disulfides (VS.sub.2, NbS.sub.2, and TaS.sub.2)
show particular promise, having a relatively low .epsilon.LUS
(<-5.8 eV) and a correspondingly strong Ea.
[0114] Next, Applicants performed a more accurate assessment of the
group 5 metal disulfides by computing the concentration-dependent
free energy of surface H adsorption, including entropic
contributions and explicit calculation of Ea. For the HER at pH=0
and at zero potential relative to the standard hydrogen electrode,
the free energy of H.sup.++e.sup.- is by definition the same as
that of 1/2H.sub.2 at standard conditions. Sabatier's principle
implies that on an optimal catalyst, the free energy of the
reaction intermediate--in this case, adsorbed H--should be close to
this value, which Applicants define to be zero (3, 10, 15, 16). In
examining concentration dependence, it is preferable to distinguish
between the total (Gtot) and differential (Gdiff) free
energies:
Gtot=(Ea+.DELTA.EZP-T.DELTA.S)*nH
Gdiff=.differential.Gtot/.differential.nH (3)
[0115] Here, .DELTA.EZP (the zero-point energy difference between
adsorbed H and 1/2H.sub.2) together with T.DELTA.S (the entropy
correction) amounts to 0.29 eV, at room temperature. According to
FIG. 9B, G.sub.tot increases monotonously with the H coverage on
the surface of group 5 disulfides. The behavior indicates that at
zero potential, dilute H adsorption is thermodynamically favored
over dense adsorption. This further justifies Applicants' choice to
focus on the low-coverage limit when considering .epsilon.LUS as a
descriptor. On the other hand, Gdiff at the equilibrium H coverage
represents the free energy cost to adsorb/desorb H on/from the
catalyst, which in turn reflects the kinetics of catalysis near
equilibrium (3, 10, 15, 16). FIG. 9C shows that at low surface
coverage, each of the group 5 disulfides has a low G.sub.diff
(<0.4 eV/H at the coverage H:M=1:16), supporting Applicants'
initial supposition that these materials are promising candidates
for surface-active HER catalysis.
[0116] Moreover, the shallow slopes of the curves in FIG. 9B below
.about.25% surface coverage indicate that low G.sub.diff will be
retained even at somewhat higher coverages. In addition, each of
the group 5 disulfides is metallic, unlike the semiconductors
MoX.sub.2 and WX.sub.2. Their higher intrinsic electronic
conductivity should further benefit their operation as
electrocatalysts.
[0117] One interesting consequence of surface activity is that for
van der Waals layered material like MX.sub.2, the H.sub.2 produced
at surface sites and trapped between layers could lead to peeling
off of the layers (FIG. 2A), analogous to chemical exfoliation by
the lithium intercalation and reaction with water (7, 21). Thinner
samples would improve the H accessibility of surface sites, and
increases the electron transfer across the layers.
[0118] Applicants tested the surface catalytic activity of group 5
MX.sub.2 on one of the representative H phase TaS.sub.2 platelets
(H--TaS.sub.2, see Examples 2.1-2.5 for details). Polarization
curve of H--TaS.sub.2 for HER electrocatalysis is measured versus
the reversible hydrogen electrode (RHE), and compared to those of
commercial H--MoS.sub.2 platelets with similar dimensions (FIG.
10A). The as-synthesized H--TaS.sub.2 platelets have lateral sizes
up to 20 .mu.m and thicknesses of 100-600 nm (FIG. 2B and FIG. 13),
and show high crystallinity according to X-ray diffraction (FIG.
13), Raman spectroscopy (FIG. 2E), and high-resolution transmission
electron microscopy (HRTEM) (FIG. 2D and FIG. 23).
[0119] H--TaS.sub.2 exhibits a nearly zero onset overpotential
after 5000 potential cycles (see Examples 2.1-2.5), similar to Pt
and far superior to H--MoS.sub.2 under identical cycling
conditions. The current density is also much higher, reaching 15
mA/cm.sup.2 at 150 mV, compared with 0.1 mA/cm.sup.2 for
H--MoS.sub.2. In FIG. 10A, Applicants also benchmark the
performance of H--TaS.sub.2 against the T phases of both MoS.sub.2
and TaS.sub.2 (T are higher in energy compared with H for both
materials (see Examples 2.1-2.5 for preparation methods).
[0120] Recent reports indicated that the T phase has higher HER
activity than the H phase in the case of MoS.sub.2 (confirmed here)
(7, 14). In contrast, the performance of H--TaS.sub.2 far exceeds
that of the T phase samples. This can be expected from their
.epsilon.LUS values: T-TaS.sub.2 has a larger .epsilon.LUS and
therefore weaker Ea than those of H--TaS.sub.2 (FIG. 8D).
[0121] Tafel plots extracted from the polarization curves (FIG.
10B) allow for quantification of the exchange current density for
each of the systems. Applicants find that H--TaS.sub.2 has an
exchange current density (9.2.times.10.sup.-4 A cm.sup.-2, FIG.
10C) that is more than 200 times higher than that of H--MoS.sub.2
and T-MoS2, and more than 10,000 times higher than that of
T-TaS.sub.2. In addition, the Tafel slope of H--TaS.sub.2 is lower
than that of H--MoS.sub.2, implying a different rate-determining
HER step. This would be expected for a shift in the catalytically
active site from a stronger-adsorption edge site (H--MoS.sub.2) to
a weaker-adsorption surface site (H--TaS.sub.2). Notably, the
H--TaS.sub.2 has the best HER activity over all the reported
MX.sub.2 materials (Table 2) in terms of onset overpotential,
exchange current density, and current density observed at 150 mV.
Collectively, the electrochemical tests for H--TaS.sub.2 are fully
consistent with an efficient surface-active HER electrocatalyst, as
predicted by Applicants' theoretical investigation.
[0122] The H--TaS.sub.2 multilayer platelets show self-improving
performance with cycling (.about.3500-fold increase in cathodic
current density after 5000 cycles, FIG. 10D and FIG. 20), as
predicted above. Raman spectra and HRTEM confirm the retaining of H
phase of TaS.sub.2 after cycling (FIGS. 2E and H). Atomic force
microscope (AFM) (FIGS. 2B and F) and TEM (FIGS. 2C and G) show the
platelets indeed become thinner, and the electron transfer charge
resistance drops by .about.600 times (FIG. 21), as a result of
exfoliation induced by surface activity. In contrast, the
performance of surface-inactive H--MoS.sub.2 retains similar
performance after cycling. Applicants point out that the
self-improving behavior requires H intercalation into the weakly
coupled interlayers, a unique property for vdW solids.
[0123] In summary, the abundance of active sites, combined with
properly tuned adsorption thermodynamics and high intrinsic
electrical conductivity, establish H phases of the group 5 metal
disulfides as promising surface-active HER electrocatalysts.
Example 2.1
Computational Details
[0124] Spin-polarized DFT calculations were performed using
Projector Augmented Wave (PAW) pseudopotentials and
Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, as
implemented in VASP. All structures are relaxed until the force on
each atom is less than 0.01 eV/.ANG.. Monkhorst-Pack (MP) k-points
sampling is used, with >15 .ANG. vacuum space in the
non-periodic direction.
[0125] For MX.sub.2 with H or T phase, E.sub.a is calculated by
using a 4.times.4 cell. For MX.sub.2 with T' phase, E.sub.a is
calculated by using a 4.times.2 3 cell. .epsilon..sub.LUS is
calculated from the unit cell. The edge is modeled by using a
nanoribbon with 4.times. 3 cell width.
Example 2.2
Synthesis of TaS.sub.2 Crystal Platelets
[0126] H--TaS.sub.2 crystal platelets are grown by a chemical vapor
deposition on SiO.sub.2/Si substrates from sulfur and tantalum
chloride powders and gaseous hydrogen precursors in a 3-stage
furnace via the following reactions:
H 2 + ( 1 8 ) S 8 .fwdarw. H 2 S ( 1 ) M Cl 5 + H 2 S + ( 1 2 ) H 2
.fwdarw. M S 2 + ( 5 ) H Cl ( 2 ) ##EQU00002##
[0127] The sulfur, tantalum chloride, and growth substrate regions
are held respectively at .about.250.degree. C., .about.300.degree.
C., and .about.750.degree. C. for a 10 minute growth period with a
20 sccm flow of Ar/H.sub.2 (85:15). 2H-TaS.sub.2 platelets can be
converted to the T phase by heating in a sulfur and argon
atmosphere at 900.degree. C. for 1 hour and then rapidly
quenching.
Example 2.3
n-Butyl Lithium Exfoliation Treatment
[0128] The thinner T-TaS.sub.2 nanosheets were obtained by soaking
the as-synthesized T-TaS.sub.2 platelets in 3 ml n-butyllithium
solution (1.6 M, Sigma-Aldrich) at room temperature for 48 hours in
a sealed vial inside an argon-filled glove box. The excess n-butyl
lithium was removed by centrifuging at 4000 rpm following rinsing
with hexane. Next, excess deionized water was added in to react
with the intercalated lithium, which generated H.sub.2 gas and
separated the 2D platelets. After exfoliation, the samples were
centrifuged at 10,000 rpm to remove unreacted precipitant and get
the suspending solution for future tests. The T-MoS.sub.2
nanosheets were prepared following the similar lithium
intercalation and water reaction procedures, but from the
commercial H--MoS.sub.2 plates (Sigma-Aldrich).
Example 2.4
Electrochemical Studies
[0129] Electrochemical measurements were performed in a
three-electrode electrochemical cell using a Autolab PGSTAT302N
potentiostat. All measurements were performed in 50 mL of 0.5 M
H.sub.2SO.sub.4 (aq) electrolyte (pH=0.16) prepared using 18
M.OMEGA. deionized water purged with Ar gas (99.999%). The glassy
carbon electrode (CH Instruments, Dia. 3 mm) casted by the samples
was employed as the working electrode while a graphite rod and a
saturated calomel electrode (SCE) (CH Instruments) was used as a
counter and a reference electrode, respectively. A glassy carbon
plate loaded with H--TaS.sub.2 samples was also employed as a
working electrode in order to monitor the morphology change during
long-time potential cycling.
[0130] The reversible hydrogen electrode (RHE) was calibrated in
the high purity H.sub.2 saturated electrolyte using platinum as
both working and counter electrode. Cyclic voltammetry (CVs) was
run at a scan rate of 1 mV s.sup.-1, and the average of the two
potentials at which the current crossed zero was taken to be the
thermodynamic potential for the hydrogen electrode reactions. In
0.5 M H.sub.2SO.sub.4, E (RHE)=E (SCE)+0.254 V.
[0131] The hydrogen evolution reaction (HER) was measured using
linear sweep voltammetry between +0.10.about.-0.50 V vs. RHE with a
scan rate of 5 mV s.sup.-1. The stability was evaluated by the
potential cycling performed using CVs initiating at +0.2 V and
ending at -0.6 V vs. RHE at either 100 mV s.sup.-1 or 5 mV
s.sup.-1. All data are corrected for a small ohmic drop using
electrochemical impedance spectroscopy (EIS). EIS was performed at
a biased potential of -0.4 V vs. RHE while sweeping the frequency
from 1 MHz to 10 mHz with a 5 mV AC amplitude.
Example 2.5
Characterizations
[0132] Scanning electron microscopy (SEM) images were recorded on
an FEI Quanta 400 microscope. Atomic force microscopy (AFM)
measurements were taken using an Agilent Picoscan5500 AFM equipped
with a silicon tapping mode tip (AppNano). In the case of comparing
the morphology before and after potential cycling, SEM and AFM
images were taken on the samples loaded onto the glassy carbon
plate. Transmission electron microscopy (TEM) images were collected
on a JEOL 2100F TEM. Samples were prepared by drop-drying a diluted
suspension in isoproponal onto copper grids covered with lacy
carbon films. X-ray diffraction (XRD) was carried out on a Rigaku
D/Max Ultima II Powder XRD. Raman spectra were carried out at an
excitation wave length of 514 nm.
TABLE-US-00002 TABLE 2 HER activity on previous reports and this
Example. Catalyst loading j.sub.0 Tafel slope j@-0.15 V vs. Sample
(.mu.g/cm.sup.2) (A/cm.sup.2) (mV/decade) RHE (mA/cm.sup.2) Ref
Nanoparticulate MoS.sub.2 N/A 1.3-3.7 .times. 10.sup.-7 55-60 0.2
(8) Particulate MoS.sub.2 4 4.6 .times. 10.sup.-6 120 0.5 (9)
Double gyroid MoS.sub.2 60 6.9 .times. 10.sup.-7 50 1 (10) Edge
exposed MoS.sub.2 film 8.5 2.2 .times. 10.sup.-6 105-120 0.06 (11)
Edge exposed MoS.sub.2 film 22 1.71-3.40 .times. 10.sup.-6 115-123
0.1 (12) 30 nm MoS.sub.2 3400-3900 5.0 .times. 10.sup.-5 66 10.3
(13) T- MoS.sub.2 50 N/A 40 1 (14) T- MoS.sub.2 N/A N/A 43 2 (15)
MoS.sub.2/RGO 285 5.1 .times. 10.sup.-6 41 8 (16) Defect-Rich
MoS.sub.2 285 8.9 .times. 10.sup.-6 50 3 (17) Electrodeposited
MoS.sub.2 N/A N/A 106 2 (18) MoS.sub.2/CNT-graphene 650 2.91
.times. 10.sup.-5 100 2 (19) NanoflakesWS.sub.2 350 N/A 48 1 (20)
WS.sub.2/RGO 400 N/A 58 2 (21) T-WS.sub.2 6.5 .sup. 1 .times.
10.sup.-6 60 1 (22) H-MoS.sub.2 100 3.4 .times. 10.sup.-6 120 0.08
This T-MoS.sub.2 50 2.5 .times. 10.sup.-6 78 0.2 Example
T-TaS.sub.2 80 6.4 .times. 10.sup.-8 92 0.02 H-TaS.sub.2 50 9.2
.times. 10.sup.-4 99 19
REFERENCES
[0133] 1. J. A. Turner, Science 305, 972 (2004). [0134] 2. M.
Chhowalla et al., Nat Chem 5, 263 (2013). [0135] 3. B. Hinnemann et
al., J. Am. Chem. Soc. 127, 5308 (2005). [0136] 4. T. F. Jaramillo
et al., Science 317, 100 (2007). [0137] 5. D. Kong et al., Nano
Lett. 13, 1341 (2013). [0138] 6. D. Voiry et al., Nat. Mater. 12,
850 (2013). [0139] 7. M. A. Lukowski et al., J. Am. Chem. Soc. 135,
10274 (2013). [0140] 8. D. J. Li et al., Nano Lett. 14, 1228
(2014). [0141] 9. Y. Yu et al., Nano Lett. 14, 553 (2014). [0142]
10. C. Tsai, F. Abild-Pedersen, J. K. Norskov, Nano Lett. 14, 1381
(2014). [0143] 11. J. Xie et al., J. Am. Chem. Soc. 135, 17881
(2013). [0144] 12. H. I. Karunadasa et al., Science 335, 698
(2012). [0145] 13. J. Kibsgaard, Z. Chen, B. N. Reinecke, T. F.
Jaramillo, Nat. Mater. 11, 963 (2012). [0146] 14. D. Voiry et al.,
Nano Lett. 13, 6222 (2013). [0147] 15. J. K. Noorskov et al., J.
Electrochem. Soc. 152, J23 (2005). [0148] 16. J. Greeley, T. F.
Jaramillo, J. Bonde, I. Chorkendorff, J. K. Norskov, Nat. Mater. 5,
909 (2006). [0149] 17. B. Hammer, J. K. Norskov, Nature 376, 238
(1995). [0150] 18. J. K. Norskov, T. Bligaard, J. Rossmeisl, C. H.
Christensen, Nat Chem 1, 37 (2009). [0151] 19. J. K. Noorskov, F.
Abild-Pedersen, F. Studt, T. Bligaard, Proc. Natl. Acad. Sci. USA
108, 937 (2011). [0152] 20. Y. Liu, Y. M. Wang, B. I. Yakobson, B.
C. Wood, Phys. Rev. Lett. 113, 028304 (2014). [0153] 21. P.
Joensen, R. F. Frindt, S. R. Morrison, Mater. Res. Bull. 21, 457
(1986).
REFERENCES
[0154] Without further elaboration, it is believed that one skilled
in the art can, using the description herein, utilize the present
disclosure to its fullest extent. The embodiments described herein
are to be construed as illustrative and not as constraining the
remainder of the disclosure in any way whatsoever. While the
embodiments have been shown and described, many variations and
modifications thereof can be made by one skilled in the art without
departing from the spirit and teachings of the invention.
Accordingly, the scope of protection is not limited by the
description set out above, but is only limited by the claims,
including all equivalents of the subject matter of the claims. The
disclosures of all patents, patent applications and publications
cited herein are hereby incorporated herein by reference, to the
extent that they provide procedural or other details consistent
with and supplementary to those set forth herein.
* * * * *