SCIENCE ADVANCES | RESEARCH ARTICLE

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Jinyan Cai1*, Yao Song1*, Yipeng Zang1, Shuwen Niu1, Yishang Wu1, Yufang Xie1, under a Creative
Xusheng Zheng2, Yun Liu1, Yue Lin1†, Xiaojing Liu1†, Gongming Wang1†, Yitai Qian1 Commons Attribution
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P-rich transition metal phosphides (TMPs) with abundant P sites have been predicted to be more favorable for License 4.0 (CC BY-NC).
hydrogen evolution reaction (HER) catalysis. However, the actual activities of P-rich TMPs do not behave as ex-
pected, and the underlying essence especially at the atomic level is also ambiguous. Our structural analysis
reveals the inferior activity could stem from the reduced overlap of atomic wave functions between metal and P

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with the increase in P contents, which consequently results in too strong P-H interaction. To this end, we used
N-induced lattice contraction to generally boost the HER catalysis of P-rich TMPs including CoP2, FeP2, NiP2, and
MoP2. Refined structural characterization and theoretical analysis indicate the N-P strong interaction could
increase the atomic wave function overlap and eventually modulate the H adsorption strength. The concept of
lattice engineering offers a new vision for tuning the catalytic activities of P-rich TMPs and beyond.

INTRODUCTION catalytic behaviors of P-rich TMPs is the presupposition for essen-

Water electrolysis, preferably powered by sustainable energy sources,
has been considered as one of the most feasible approaches to achieve
scalable and renewable hydrogen production (1–4). However, the
sluggish kinetics and the associated substantial energy losses severely
impede the energy conversion efficiency, which imperatively demand
efficient water electrolysis catalysts (5–7). Pt-based materials, as the
state-of-the-art hydrogen evolution reaction (HER) catalysts, are
seriously constrained by the crustal scarcity and high cost (8, 9). To
this end, many researchers have been dedicated to exploring in-
expensive and earth-abundant non-noble metal-based HER catalysts,
such as transition metal oxides (10–12), phosphides (13–16), chalco-
genides (17–19), nitrides (20–22), and carbides (23–25). Although
notable processes have been achieved in the past decades, their
performance is still far less than that of Pt, especially at acidic con-
dition, and searching new catalysts is still the primary goal (26).
Very recently, transition metal phosphides (TMPs) attract special
attention for HER catalysis, due to their diverse compositions,
unique catalytic surface, excellent chemical stability, and electrical
conductivity (1, 27). Typically, the negatively charged P sites with
moderate electronegativity could act as Lewis bases to trap the posi-
tively charged protons, potentially endowing the TMPs with a Gibbs
free energy of adsorbed H (Had) close to zero. For this reason, it has
been consciously predicted that the HER performance of TMPs could
be further boosted with the increase in P contents in the TMPs (28–30).
For instance, Pan et al. (31) found that CoP nanoparticles exhibited
significantly higher catalytic activity than Co2P. However, as ratio
of P was further increased, the HER performance of TMPs was
not promoted as expected (1, 32). The reason for the inferior HER
activities of the P-rich phosphides is actually still ambiguous, espe-
cially at the atomic level. Undoubtedly, unraveling the underlying
1
Hefei National Laboratory for Physical Science at the Microscale, Department of
Applied Chemistry, University of Science and Technology of China, Hefei, Anhui
230026, P. R. China. 2National Synchrotron Radiation Laboratory, University of Science
and Technology of China, Hefei, Anhui 230029, P. R. China.
*These authors contributed equally to this work.
†Corresponding author. Email: wanggm@ustc.edu.cn (G.W.); liuxj206@ustc.edu.cn (X.L.);
linyue@ustc.edu.cn (Y.Lin)
tially unlocking the limiting factors for HER catalysis and eventually
constructing superior HER catalysts, but unfortunately they have
been rarely studied so far.
Here, we take CoP2, a typical P-rich metal phosphide, as an example
to investigate the catalytic performance of P-rich TMPs. According
to the bond order conservation principle, the increase in P contents
will correspondingly reduce the overlap of atomic wave functions,
which typically results in strong interaction between P-rich TMPs
and Had and eventually hinders the intrinsic HER activities. So, the
limitation of P-rich TMPs for HER catalysis is probably attributed
to the decrease in intrinsic per-site activity. Structural analysis reveals
that CoP2 has a unique crystal structure, where each Co is coordinated
with six P atoms to form a slightly distorted octahedron (Fig. 1A),
and the distorted octahedrons are connected by the P─P covalent
bond illustrated by the electron density map in Fig. 1B. Therefore,
from the structural perspective, modulating the nonpolar P-P inter-
action to tailor the overlap of atomic wave functions is the key to
further boost the intrinsic HER activity of CoP2.
In this work, we rationally incorporate nitrogen into the CoP2
structures to increase the overlap of atomic wave functions via the
N-induced lattice contraction. Excitingly, the N-modified CoP2
(N-CoP2) nanowires (NWs) display an impressive overpotential of
38 mV at 10 mA cm−2, which is substantially smaller than the CoP2
NWs and even close to the benchmark Pt/C catalysts. Refined structural
characterization and theoretical calculations consistently reveal that
the created P─N bonds in N-CoP2 could bring lattice contraction to
increase the atomic wave function overlap, which consequently
broadens the local energy bandwidth with the downshift of the valence
band center and correspondingly decreases the electron coupling be-
tween CoP2 and Had to facilitate the HER catalysis. We also demon-
strate that the N-P strong interaction can generally boost the HER
activities of a variety of P-rich TMPs including CoP2, FeP2, NiP2,
and MoP2. Using lattice engineering for band structure tuning pro-
vides a new pathway to the rational construction of superior HER
catalysts and beyond.
The N-CoP2 NWs are fabricated via a three-step process, as
illustrated in Fig. 2A. Typically, Co (CO3)xOHy NWs are first grown

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SCIENCE ADVANCES | RESEARCH ARTICLE

Fig. 1. Structure analysis. (A) Crystal structure of CoP2. (B) Electron density distribution between the octahedral units.

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Fig. 2. Material synthesis and structural characterization. (A) Schematic illustration of the preparation of N-CoP2 NWs. (B) SEM image of N-CoP2 NWs on CC. (C) XRD patterns
of CoP2 and N-CoP2 NWs and the corresponding magnification of the diffraction peaks of the (200) facet. (D) HAADF-STEM image and EDX elemental mapping of Co, P, and N
for a single N-CoP2 NW. (E and F) Atomic resolution HAADF images and the corresponding strain tensor mapping and the line profile analysis for CoP2 and N-CoP2, respectively.

on carbon cloth (CC) using a well-developed hydrothermal reaction
(33). Then, the prepared Co(CO3)xOHy NWs are converted to CoP2
NWs through a thermal phosphidation process in a home-built tube
furnace system. Last, nitrogen is incorporated by calcining the CoP2
NWs in ammonia atmosphere. Figure S1 presents the SEM images
of the prepared Co(CO3)xOHy, which show that the entire CC is
uniformly covered with well-aligned NW arrays. Even after the
phosphidation and the consequent nitrogen incorporation, the NW
morphology still can be preserved (Fig. 2B and fig. S2). Meanwhile,
the transmission electron microscopy images (fig. S3) indicate that
the smooth NW becomes rougher after these thermal treatments. In
addition, x-ray diffraction (XRD) is used to acquire the structural
information. The diffraction peaks located at around 24.8°, 35.2°, 35.6°,
and 37.6° correspond to the (−111), (002), (200), and (−121) planes,
respectively, of the monoclinic CoP2 (Joint Committee on Powder
Diffraction Standards no. 77-0263). CoP2 and N-CoP2 NWs prepared
at 350°C show very similar diffraction patterns, while the diffraction
peaks have slightly shifted to the higher angle region with the N in-
corporation (Fig. 2C and fig. S4), suggesting that N doping does not
intrinsically change the structures of CoP2 but leads to the slightly
compressed interplanar distances. Moreover, with the further in-
crease in the ammonia treatment temperatures, N-CoP2 eventually
undergoes phase segregation to form the mixture of CoP2 and CoP
(fig. S5). The energy-dispersive x-ray (EDX) spectrum of N-CoP2
reveals the atomic ratio of Co, P, and N is around 1:1.74:0.3 (fig. S6).
In addition, the high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) and the corresponding EDX
elemental mapping images indicate that Co, P, and N are homoge-
neously distributed over the NW (Fig. 2D). Meanwhile, the atomic
resolution HAADF analysis in Fig. 2 (E and F) reveals that the in-
corporation of N into CoP2 results in the decreased d-spacing of the
(002) and (020) facets, which is consistent with the peak shift toward
higher angles in the XRD patterns. The quantified structure con-
traction parameters estimated by atomic resolved HAADF and XRD
characterizations are listed in table S1. Moreover, the strain tensor
values using the geometric-phase analysis of N-CoP2 are more neg-
ative than those of CoP2, proving that N doping gives rise to the
lattice contraction in N-CoP2.

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SCIENCE ADVANCES | RESEARCH ARTICLE
To unravel the effects of N dopants on the electronic structures
of CoP2, x-ray photoelectron spectroscopy (XPS) is further conducted.
Figure 3A presents the typical XPS Co 2p spectra of CoP2 and N-CoP2.
The peaks located at ~778.59 and 793.60 eV are ascribed to the Co
2p3/2 and Co 2p1/2 of the Co─P bonds, respectively (32, 34). After N
doping at 350°C, the binding energies of Co 2p3/2 and Co 2p1/2 only
exhibit a very slight shift to the lower energy region. Moreover, with
the increase in the ammonia treatment temperatures, gradual shifts
are observed (fig. S7A), which may be originated from the created
intrinsic defects, due to the reducing property of the ammonia.
Meanwhile, the XPS P 2p spectra in Fig. 3B can be deconvoluted into
a pair of peaks, which correspond to the P 2p3/2 and P 2p1/2 of the
Co─P bonds (30, 35). Impressively, the peak positions of the P 2p
were gradually shifted to the higher binding energy region, with the
incorporation of nitrogen (Fig. 3B and fig. S7B), indicating the
decreased average electron density around the P sites in N-CoP2,
which is probably induced by the N-P strong interaction. Moreover,
the broad XPS N 1s spectrum of N-CoP2 can also be deconvoluted
into the chemical states of N-Co and N-P (Fig. 3C and fig. S7C),
suggesting that N is successfully doped into the CoP2 lattices.
Furthermore, synchrotron-based x-ray absorption fine structure
(XAFS) spectroscopy is used to probe the localized coordination
environments of the Co sites in the N-CoP2. The x-ray absorption
near-edge spectra (XANES) of CoP2 and N-CoP2 with standard Co
foil and Co2O3 as references are shown in fig. S8A. The pre-edge of
CoP2 slightly shifts to the lower energy values after N doping, which
suggests the increased average electron densities around the Co
sites. In addition, Co L-edge XANES for surface chemical electronic
state characterization is also measured using soft x-ray (fig. S8B), in
which the reduced intensity of the L3-edge peak of N-CoP2 also suggests
more electron filling of the Co d orbital (36). This is in agreement
with the XPS Co 2p and XANES Co K-edge results. The similar
oscillation profiles of the extended x-ray absorption fine structure
(EXAFS) analysis of k2-weighted (k) signals (fig. S8C) indicate that
the overall crystal structure of CoP2 is well maintained after N doping,
Fig. 3. XPS and XAFS characterization. (A) XPS Co 2p spectra and (B) XPS P 2p spectra of CoP2 and N-CoP2. (C) XPS N 1s spectrum of N-CoP2. (D) k2-weighted FT-EXAFS
curves of the Co K-edges for CoP2 and N-CoP2. WT-EXAFS spectra of (E) CoP2 and (F) N-CoP2. a.u., arbitrary units.
Cai et al., Sci. Adv. 2020; 6 : eaaw8113 3 January 2020
consistent with the XRD results in Fig. 2C. Figure 3D shows the
corresponding R space curves of Co after k2[(k)]-weighted Fourier
transform, where the single strong shell at around 1.78 Å originated
from the Co-P vector (fig. S9A). For N-CoP2, the shell becomes
slightly broader, which may be attributed to the formation of a
Co-N vector with very similar peak position at around 1.78 Å
(fig. S9B) (37). Because of the slight bond length difference between
Co-N and Co-P, more-refined first shell analysis of CoP2 and N-CoP2
is further carried out. Figure 3 (E and F) shows the wavelet trans-
form (WT) contour plots of the two signals based on Morlet wavelets
with optimum resolution at the first shell. Apparently, CoP2 has the
maximum intensity at k = 4.95 Å−1, while the maximum of N-CoP2
presents at k = 4.90 Å−1. The small shift of the WT maximum mostly
originated from the atomic number difference between P and N
(fig. S10) (38). Together, XPS and XAFS analyses further demonstrate that
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N is substitutionally doped into the structure of CoP2, which can es-
sentially manipulate the electronic and coordination structures of CoP2.
The catalytic performance for HER catalysis is evaluated in a
typical three-electrode configuration with 0.5 M H2SO4 as the electro-
lyte. For the sake of comparison, bare CC, CoP2, and Pt/C are also
examined. Figure 4A shows the linear sweep voltammetry (LSV)
curves at the scan rate of 5 mV s−1. Impressively, N-CoP2 displays
the best electrocatalytic activity with an overpotential of only 38 mV at
10 mA cm−2, which is substantially smaller than those of CC (458 mV)
and CoP2 (125 mV), and even close to the performance of the
benchmark Pt/C (28 mV). It also represents the best performance
toward HER catalysis in acidic conditions among reported Co-based
compounds (13, 19, 39). The temperature-dependent activities of
N-CoP2 (denoted as N-CoP2-X) with various N concentrations [N/
(N + P)] quantified by XPS characterizations are also studied and
shown in Fig. 4B, fig. S11, and table S2. The maximum HER activity
was achieved at the temperature of 350°C with an N content of
17.1%. With further increase in the temperature and N contents,
the HER activity begins to decay, which may be attributed to the
unfavorable phase segregation to form CoP (figs. S5 and S12). To
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Fig. 4. Electrochemical HER performance. (A) LSV curves for CC, CoP2, N-CoP2, and Pt/C in 0.5 M H2SO4. (B) The overpotentials at 10 mA cm−2 for CoP2, N-CoP2-250,
N-CoP2-350, N-CoP2-450, and N-CoP2-550. (C) The corresponding Tafel plots for CC, CoP2, N-CoP2, and Pt/C. (D) TOF plots of CoP2 and N-CoP2 against the potentials for
HER. CPE, constant phase element. (E) Nyquist plots of CoP2 and N-CoP2 at 100 mV versus RHE. (F) Chronopotentiometric curve for N-CoP2 at the current density of 20 mA cm−2.
The insets are the SEM images of N-CoP2 before and after the stability test.
further probe the catalytic kinetics, Tafel plots derived from the po-
larization curves are provided in Fig. 4C. The measured Tafel slope
for the N-CoP2 is 46 mV dec−1, much smaller than the 73 mV dec−1
of the CoP2, which proceeds via the Volmer-Heyrovsky mechanism
with Heyrovsky step [Had + H+ + e− → H2] as the rate-determining step.
To deeply evaluate the correlation of Tafel slopes and the catalytic
kinetics, we investigate the hydrogen oxidization reaction (HOR)
mechanism experimentally. The measured Tafel slopes of CoP2 and
N-CoP2 for HOR are 207 and 341 mV dec−1, respectively, which
proceed with the Heyrovsky-Volmer mechanism and the Heyrovsky
step [H2 → Had + H+ + e−] as the rate-determining step (fig. S13 and
table S3). Together, all these results consistently demonstrate N-CoP2
has superior HER catalytic kinetics due to the accelerated rate-­
determining Heyrovsky step with weakened adsorption strength
between Had and the catalyst surface (40, 41).
Since the surface area variation may also affect the HER activity,
cyclic voltammetry (CV) studies are used to estimate the electro-
chemical surface areas by measuring the electrochemical double-­
layer capacitance (Cdl), as shown in fig. S14C. The calculated Cdl of
N-CoP2 is 10.8 mF cm−2, which is larger than the 6.1 mF cm−2 of
CoP2. However, the catalytic current of N-CoP2 at 50 mV is 32 times
higher than that of CoP2, implying the enhanced HER activity did
not mainly stem from the increased surface area. To further probe
the intrinsic per-site catalytic activity, turnover frequency (TOF) is
plotted in Fig. 4D (42). Apparently, the TOF values of N-CoP2 are
consistently larger than those of CoP2 in the whole studied potential
region, suggesting that the catalytic surface of CoP2 has been essentially
changed after nitrogen incorporation. Furthermore, electrochemical
impedance spectroscopy (EIS) is used to explore the interfacial
charge transfer kinetics on the catalytic surface. Figure 4E shows the
Nyquist plots of CoP2 and N-CoP2 at 100 mV versus Reversible
Hydrogen Electrode (RHE), respectively. Both the Nyquist plots
present typical semicircle profiles from 100 kHz to 0.01 Hz, which
can be well fitted using a simplified Randle circuit model (Fig. 4E,
Cai et al., Sci. Adv. 2020; 6 : eaaw8113 3 January 2020
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inset). The fitted charge transfer resistance (Rct) for N-CoP2 (2 ohm)
is much smaller than that of CoP2 (13 ohm), suggesting that N dop-
ing could accelerate the interfacial charge transfer kinetics. Last, the
electrochemical stability of N-CoP2 is also evaluated. Figure 4F shows
the chronopotentiometric curve of N-CoP2 at the current density
of 20 mA cm−2. The overpotential change (versus RHE) during the
chronopotentiometric test goes from −53.2 to −64.6 mV in 30 hours.
The decay mainly occurs in the first 12 hours, and then the potential
becomes relatively stable. The initial decay could be attributed to the
generated bubbles that cannot be efficiently released from the elec-
trode surface. Furthermore, the SEM image and XRD pattern are
also collected after the stability testing, as shown in the insets of
Fig. 4F and fig. S15. Both the NW morphology and the crystal struc-
ture can be well maintained after the durability testing, further indi-
cating the robustness of N-CoP2 NWs for HER catalysis.
Density functional theory (DFT) is further carried out to study
the possible effects of nitrogen doping on the HER activity of CoP2.
Figure 5A shows the crystal structures of CoP2 and N-CoP2 with
labeled lattice constants. The decreased lattice constants after N
incorporation reveal the existence of remarkable lattice contraction,
which stemmed from the formation of shorter and stronger N─P
bonds as junctions of the octahedral units in the N-CoP2. Meanwhile,
the mapping of orbital wave functions in Fig. 5A illustrates the strong
N-P interaction results in substantially increased atomic orbital wave
function overlap integrals, especially between N and P by the  type
overlap with the decreased principle quantum number for the involved
N atomic orbitals. Moreover, the more localized electron density and
the decreased bond lengths in the surface models of N-CoP2 with
various facets of (100), (001), and (010) (Fig. 5B and figs. S16 and S17)
relative to those of CoP2 further support that the N-P interaction is
much stronger than the P-P interaction. The increased atomic wave
function overlap integrals spread the large energy difference between
the highest and lowest orbital levels in the local band and further
broaden the local energy bandwidth (43, 44). Figure 5C illustrates
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Fig. 5. DFT calculations. (A) Crystal structures of CoP2 and N-CoP2 with lattice constants and the corresponding mapping of orbital wave functions. (B) Surface electron
density difference of CoP2 (100) and N-CoP2 (100). (C) DOS of CoP2 and N-CoP2 with/without hydrogen adsorption and the schematic diagram of the relation between the
broadened bandwidth and H adsorption strength. (D) Calculated GH* on CoP2 and N-CoP2 with various facets.
how the energy levels and bandwidths vary with the internuclear
distance of atoms in a crystalline solid, in which the shaded areas
represent the energy bands formed by the valence orbitals. As the
internuclear distance decreases, the collection of valence orbitals
gradually broadens into bands, where the formed overlapped bands
(the intermix) further broaden the bandwidth. As the bandwidth
widens, the only way to maintain the number of fixed valence elec-
trons is to shift the valence band center of CoP2 away from the Fermi
level, which is also reflected by the density of states (DOS) with the
shifted valence band center from −1.32 to −1.36 eV (Fig. 5C). Ac-
cording to the Newns-Anderson model that expresses the adsorption
energies depend on the interactions between the catalyst valence bands
and the adsorbate orbitals, the electron coupling between them gives
rise to the bonding and antibonding state splitting, as illustrated in
Fig. 5C. Since the wave function of high-lying antibonding states has
dominant catalyst valence states characters, the downshift of the CoP2
hybridization valence band center will correspondingly reduce the
antibonding level relative to the Fermi level (Fig. 5C and fig. S18)
and consequently lead to the weak adsorption strength that origi-
nated from more electron fillings of antibonding states (fig. S19). We
also study the effects of N concentration on the calculated adsorption
energies of hydrogen (GH*), the GH* on the various crystal facets of
N-CoP2 with different N concentrations are consistently much closer
to neutral than those on the CoP2 (Fig. 5D and figs. S20 and S21).
Moreover, the interplanar distances of various crystal facets of N-CoP2
are also consistently decreased (table S4). Typically, the GH* close to
neutral is the key descriptor for HER catalysis in acidic condition.
Therefore, the smaller GH* value induced by the strong N-P inter-
action enables N-CoP2 to be highly active for HER catalysis.
Since intrinsic defects may also be created during the ammonia
treatment, we further theoretically and experimentally study the effects
of the defects on the HER catalysis of CoP2. As shown in fig. S22A,
although the GH* value of the defective CoP2 is closer to neutral
than that of CoP2, it is still much inferior to that of N-CoP2. Meanwhile,
defects in CoP2 are also intentionally introduced by hydrogen treatment
and experimentally evaluated for HER catalysis. Electrochemical
Cai et al., Sci. Adv. 2020; 6 : eaaw8113 3 January 2020
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characterization indicates that the HER activity of CoP2 can be
improved with the introduction of defects (fig. S22B). However,
considering that the performance of defective CoP2 (D-CoP2) is still
far less than that of N-CoP2, it suggests that the exceptionally high
HER activity of the N-CoP2 did not mainly stem from the intrinsic
defects but the N-induced lattice contraction.
In view of the existence of P─P bonds in many P-rich TMPs, we
also evaluate the feasibility of nitrogen doping for improving the
HER catalysis of other P-rich TMPs including of FeP2, NiP2, and
MoP2. Figures S23 and S24 show the crystal structures and the pro-
jected density of state (PDOS) plots of FeP2, NiP2, MoP2, and their
corresponding N-doped counterparts. Similarly, all of them consist­
ently undergo lattice contraction with increased atomic wave func-
tion overlap integrals, which consequently result in broadened energy
bandwidths and the downshift of the valence band centers by the
formation of N-P strong interactions. To further prove the feasibility
for HER catalysis, we experimentally fabricated these P-rich metal
phosphides and studied their electrochemical properties including
LSV, Tafel, and stability (figs. S25 to S27). The electrochemical studies
consistently indicate that the N doping can substantially improve the
HER performances of FeP2, NiP2, and MoP2 with overpotentials of
97, 153, and 135 mV, respectively, at the current of 10 mA cm−2.
These results suggest that lattice contraction induced by the N-P
strong interactions is a general strategy to boost the HER catalysis
of P-rich TMPs.
In summary, we have demonstrated that the HER performance
of P-rich CoP2 can be significantly boosted by N-induced lattice
contraction. The prepared N-CoP2 exhibits an impressive over-
potential of 38 mV at 10 mA cm−2, which is very close to that of
precious Pt catalysts in acidic conditions and also represents the best
activity among reported Co-based catalysts. Refined structural char-
acterization and DFT calculation consistently reveal that the created
strong N-P interaction in CoP2 could increase the atomic wave func-
tion overlap via the lattice contraction and consequently broaden the
local energy bandwidth with the downshift of the valence band center,
which eventually facilitate the HER catalysis by weakening the electron
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coupling between CoP2 and Had. The lattice contraction strategy via
N-P strong interactions can generally boost the HER catalysis of a
variety of P-rich TMPs including CoP2, FeP2, NiP2, and MoP2, of-
fering a new lattice engineering approach to fundamentally tuning
the electronic properties of P-rich TMPs for HER catalysis and
beyond.
MATERIALS AND METHODS
The synthesis of CoP2 and N-CoP2 NWs
CoP 2 NWs were fabricated by the thermal phosphidation of
Co(CO3)xOHy NWs. The Co(CO3)xOHy NWs were first grown
on CC by a conventional hydrothermal reaction (33). Typically,
1 mmol of Co(NO3)2·6H2O, 5 mmol of CO(NH2)2, and 2 mmol
NH4F were dissolved in 20 ml of deionized water under vigorous
stirring. Then, the prepared homogeneous solution was transferred
into a 25-ml Teflon-lined autoclave with a piece of hydrophilic CC
placed against the wall of the autoclave. Last, the reaction solution
was maintained at 120°C for 4 hours to synthesize the Co(CO3)xOHy
NWs on CC. The as-synthesized Co(CO3)xOHy was washed with water
and ethanol several times and lastly dried under a vacuum oven.
The phosphidation treatment was conducted at 550°C for 3 hours
in a tube furnace system with red phosphorus as the P source and
argon gas as the carrier gas. N-doped CoP2 NWs (N-CoP2) were
achieved by annealing the CoP2 under ammonia condition at various
temperatures (250° to 550°C with interval of 100°C) for 20 min.
Synthesis of N-FeP2, N-NiP2, and N-MoP2
The P-rich metal phosphides including FeP2, NiP2, and MoP2 were
prepared using a similar method used for CoP2. FeOOH, Ni(OH)2,
and MoS2 for the following the phosphidation treatment were syn-
thesized using previously reported methods (45–47). FeP2 and NiP2
were achieved at the phosphidation temperature of 550°C for
3 hours, while MoP2 was obtained at the temperature of 800°C for
2 hours. N doping for FeP2, NiP2, and MoP2 was performed at
350°C for 30 min, 300°C for 30 min, and 550°C for 20 min, respec-
tively, under ammonia condition.
Material characterization
XRD was conducted on a Philips X’Pert Pro Super diffractometer
(with Cu K,  = 1.54182 Å). The XPS was performed at the photo-
emission end-station (BL10B) in the National Synchrotron Radiation
Laboratory, Hefei. Field emission scanning electron microscopy was
carried out on the JEOL-JSM-6700F, while the high-resolution trans-
mission electron microscopy, HAADF-STEM, and energy-dispersive
spectroscopy (EDS) mapping analyses were performed on the JEOL
JEM-ARF200F TEM/STEM with a spherical aberration corrector.
The XAFS spectra were collected at the 14W1 station in the Shanghai
Synchrotron Radiation Facility. The collected EXAFS data were
analyzed using the ATHENA program as implemented in the IFEFFIT
software packages according to the standard procedures. The k2-weighted
EXAFS spectra were achieved by pre-edge background deduction
and then normalized relative to the edge-jump step, and the plotting
k-weight was 2.
Electrochemical characterization
All the electrochemical tests were performed on a CHI 760E electro-
chemical workstation (CH Instruments, China) at room temperature.
The HER catalysis was evaluated in a three-electrode setup with
Cai et al., Sci. Adv. 2020; 6 : eaaw8113 3 January 2020
0.5 M H2SO4 solution as the electrolyte, a standard Ag/AgCl electrode
(saturated KCl solution) as the reference electrode, and a graphite
rod as the counter electrode. In the electrochemical testing, the
measured potentials were calibrated with respect to RHE. The con-
version equation is E(RHE) = E(Ag/AgCl) + 0.197 V + 0.059 × PH. The
EIS was tested at the overpotential of 100 mV versus RHE, with the
frequencies varying from 100 kHz to 0.01 Hz. All potentials were
also corrected by eliminating the electrolyte resistances obtained from
the EIS spectra. The TOF values were estimated according to the
previous reported method (48), and the specific crystal parameters
of different materials are listed in table S5. The most active sites are
supposed to be P, while the Co and N sites are relatively inactive.
Typically, the HER activity is the average results of various sites. Thus,
for TOF calculation, we consider all the possible sites as the number
of active sites, because such calculation will not overestimate the
Downloaded from https://www.science.org at Indian Institute of Technology, Kharagpur on September 22, 2022
per-site activity.
Computational details
DFT calculation was performed using the CASTEP program with
ultrasoft pseudopotentials as implemented in the Materials Studios
package of Accelrys Inc. (49). The electron exchange-correlation
potential was dealt with the Perdew-Burke-Ernzerhof functional of
generalized gradient approximation. The core electrons of atoms were
treated using effective core potential. The smooth parts of the wave
functions were expanded with a kinetic energy cutoff of 400 eV. The
5 × 5 × 5 and 2 × 2 × 1 Monkhorst-Pack mesh k-points were adopted
for Brillouin zone sampling of bulk and surface calculations, in which
the k-points are 63 and 2, respectively. The convergence criterions
were set to 5.0 × 10−6 eV per atom for energy, 5.0 × 10−4 Å for maximum
displacement, and 0.01 eV Å−1 for maximum force. The lattice
parameters of the CoP2 unit cell after geometry optimization were
a = 5.52 Å, b = 5.53 Å, c = 5.59 Å, which were comparable with the
experimental data (a = 5.55 Å, b = 5.55 Å, c = 5.61 Å). The surfaces
(001), (010), and (100) were modeled by a periodic slab repeated in
a 2 by 2 by 2 surface unit cell with a vacuum region of 12 Å between
the slabs along the z axis. The whole configuration in all the calcula-
tions was relaxed during the geometry optimizations and was carried
out in the reciprocal space. The free energy of Had was determined
according to the previous report (50). The same calculation parameters
as CoP2 were also applied for FeP2, NiP2, and MoP2, and the used
crystal parameters of the unit cells are listed in table S6.
SUPPLEMENTARY MATERIALS
Supplementary material for this article is available at http://advances.sciencemag.org/cgi/
content/full/6/1/eaaw8113/DC1
Fig. S1. SEM images of Co(CO3)xOHy NWs collected with different magnifications.
Fig. S2. The influence of ammonia treatment temperature on the morphology of N-CoP2-X (X is
the temperature).
Fig. S3. Structure characterizations of Co(CO3)xOHy, CoP2, and N-CoP2.
Fig. S4. The magnified XRD patterns of CoP2 and N-CoP2.
Fig. S5. The influence of ammonia treatment temperature on the composition of N-CoP2-X (X is
the temperature).
Fig. S6. Elemental composition characterization of N-CoP2 NWs.
Fig. S7. XPS spectra of Co 2p, P 2p, and N 1s.
Fig. S8. XAFS and XANES characterizations of CoP2 and N-CoP2.
Fig. S9. The k2-weighted FT-EXAFS curves of CoP2 and N-CoP2 with CoP and CoNx as reference.
Fig. S10. WT-EXAFS of CoP and CoNx.
Fig. S11. The electrochemical HER performances of N-CoP2-X (X = 250, 350, 450, and 550) in
0.5 M H2SO4.
Fig. S12. The influences of N contents on the overpotentials of N-CoP2-X (X = 250, 350, 450,
and 550).
Fig. S13. The electrochemical HOR performances of CoP2 and N-CoP2 in 0.5 M H2SO4.
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SCIENCE ADVANCES | RESEARCH ARTICLE
Fig. S14. CV curves at different scan rates and the capacitive currents as a function of scan rate
in 0.5 M H2SO4.
Fig. S15. The XRD patterns of N-CoP2 before and after the durability test.
Fig. S16. The electron density differences of CoP2 and N-CoP2.
Fig. S17. The optimized structures of CoP2 and N-CoP2 surfaces.
Fig. S18. The PDOS of CoP2 and N-CoP2 with different surfaces.
Fig. S19. The PDOS of CoP2 and N-CoP2 with the hydrogen adsorbed on different surfaces.
Fig. S20. The optimized surface models of CoP2 and N-CoP2 with hydrogen adsorbed on
different surfaces.
Fig. S21. The calculated GH* on CoP2 and N-CoP2 with various N concentrations on different facets.
Fig. S22. The calculated GH* and LSV curves in 0.5 M H2SO4 for CoP2, D-CoP2, and N-CoP2.
Fig. S23. The optimized crystal structures of FeP2/N-FeP2, NiP2/N-NiP2, and MoP2/N-MoP2.
Fig. S24. The PDOS of FeP2/N-FeP2, NiP2/N-NiP2, and MoP2/N-MoP2.
Fig. S25. The morphology characterizations and electrochemical HER performances of FeP2
and N-FeP2.
Fig. S26. The morphology characterizations and electrochemical HER performances of NiP2
and N-NiP2.
Fig. S27. The morphology characterizations and electrochemical HER performances of MoP2
and N-MoP2.
Table S1. HAADF and XRD calculated lattice contraction for (020) and (002) facets.
Table S2. N contents acquired from XPS characterization for N-CoP2 with various treatment
temperatures.
Table S3. Tafel slopes for HOR with various mechanisms.
Table S4. The derived strain for (020) and (002) by the DFT calculation with various N contents.
Table S5. Crystallographic data of CoP2 and N-CoP2 used for calculating the number of active sites.
Table S6. Crystallographic data of FeP2/N-FeP2, NiP2/N-NiP2, and MoP2/N-MoP2.
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Acknowledgments: We acknowledge the Beamline BL14W1 at Shanghai Synchrotron
Radiation Facility for XAS characterizations. The numerical calculations in this paper were
performed on the supercomputing system in the Supercomputing Center of University of
Science and Technology of China. Funding: This work was supported by the National Key
Research and Development Program of China (2017YFA0206703), the Natural Science Fund
of China (nos. 21771169, 11722543, and 11505187), the Fundamental Research Funds for the
Central Universities (WK2060190074, WK2060190081, and WK2310000066), and the
Recruitment Program of Global Expert. Author contributions: G.W., Y.Q., X.L., and Y.Lin
designed and supervised the project. J.C. and Y.S. conducted the project. X.Z., Y.Z., and Y.W.
provided the XAFS and XPS measurements and analysis. S.N., Y.X., and Y.Liu helped in the
material synthesis. G.W., X.L., J.C., and Y.S. wrote and revised the manuscript. Competing
interests: The authors declare that they have no competing interests. Data and materials
availability: All data needed to evaluate the conclusions in the paper are present in the
paper and/or the Supplementary Materials. Additional data related to this paper may be
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requested from the authors.
Submitted 27 January 2019
Accepted 7 November 2019
Published 3 January 2020
10.1126/sciadv.aaw8113
Citation: J. Cai, Y. Song, Y. Zang, S. Niu, Y. Wu, Y. Xie, X. Zheng, Y. Liu, Y. Lin, X. Liu, G. Wang,
Y. Qian, N-induced lattice contraction generally boosts the hydrogen evolution catalysis of
P-rich metal phosphides. Sci. Adv. 6, eaaw8113 (2020).
8 of 8
 N-induced lattice contraction generally boosts the hydrogen evolution catalysis of
P-rich metal phosphides
Jinyan CaiYao SongYipeng ZangShuwen NiuYishang WuYufang XieXusheng ZhengYun LiuYue LinXiaojing LiuGongming
WangYitai Qian

Sci. Adv., 6 (1), eaaw8113. • DOI: 10.1126/sciadv.aaw8113

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