优化金属磷化物电催化析氢性能的策略

doi:10.1016/S1872-2067(21)63855-X

催化学报 ›› 2021, Vol. 42 ›› Issue (11): 1876-1902.DOI: 10.1016/S1872-2067(21)63855-X

优化金属磷化物电催化析氢性能的策略

于文丽^a, 高玉肖^a, 陈智^a, 赵莹^a, 吴则星^a^,^*(), 王磊^a^,^b^,^#()

^a生态化工教育部重点实验室, 青岛科技大学化学与分子工程学院, 山东青岛266042
^b山东省海洋环境腐蚀与安全防护工程研究中心, 青岛科技大学环境与安全工程学院, 山东青岛266042

收稿日期:2021-02-27 修回日期:2021-02-27 接受日期:2021-05-21 出版日期:2021-11-18 发布日期:2021-06-08
通讯作者: 吴则星,王磊
基金资助:
国家自然科学基金(22002068);国家自然科学基金(51772162);国家自然科学基金(52072197);山东省高校青年创新技术基金(2019KJC004);山东省杰出青年基金(ZR2019JQ14);泰山学者青年专家计划(tsqn201909114);重大科技创新项目(2019JZZY020405);山东省自然科学基金重大基础研究项目(ZR2020ZD09);山东省自然科学基金(ZR2019BB002);山东省自然科学基金(ZR2018BB031)

Strategies on improving the electrocatalytic hydrogen evolution performances of metal phosphides

Wenli Yu^a, Yuxiao Gao^a, Zhi Chen^a, Ying Zhao^a, Zexing Wu^a^,^*(), Lei Wang^a^,^b^,^#()

^aState Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China
^bShandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China

Received:2021-02-27 Revised:2021-02-27 Accepted:2021-05-21 Online:2021-11-18 Published:2021-06-08
Contact: Zexing Wu,Lei Wang
About author:^#Tel/Fax: +86-532-84022016; E-mail: inor-chemwl@126.com
^*Tel/Fax: +86-532-84022016; E-mail: splswzx@qust.edu.cn;
Lei Wang (College of Environment and Safety Engineering, Qingdao University of Science and Technology) was invited as a young member of 6th Editorial Board (2020‒2024) of Chin. J Catal. in 2020. Professor Lei Wang received his Ph.D degree in 2006 from Jilin University. Afterward, he joined the faculty of Qingdao University of Science and Technology, where he was the deputy director of Key Laboratory of Eco‐Chemical Engineering, and he is now the director of College of Environment and Safety Engineering. From 2008 to 2010, he worked as a postdoctoral fellow in the State Key Laboratory of Crystal Materials, Shandong University. His research interests currently focus on the design and synthesis of porous MOFs materials and functional inorganic materials, as well as their applications in gas separation, photocatalysis, lithium‐ion battery, etc. Professor Lei Wang has published more than 200 papers, including Nat. Commun., Adv. Energy Mater., Adv. Funct. Mater., etc.
Supported by:
National Natural Science Foundation of China(22002068);National Natural Science Foundation of China(51772162);National Natural Science Foundation of China(52072197);Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China(2019KJC004);Outstanding Youth Foundation of Shandong Province, China(ZR2019JQ14);Taishan Scholar Young Talent Program(tsqn201909114);Major Scientific and Technological Innovation Project(2019JZZY020405);Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09);Natural Science Foundation of Shandong Province, China(ZR2019BB002);Natural Science Foundation of Shandong Province, China(ZR2018BB031)

摘要/Abstract

摘要：

日益严重的能源危机和环境污染问题使得探索清洁的可再生能源载体及减少对传统化石燃料的过度依赖成为人们面临的一项重要任务. 因此, 各种可持续能源如太阳能、风能、海洋能和生物质能等得到了广泛研究并取得了一定的进展. 然而, 这些能源因存在间歇性和不稳定性等缺点阻碍了其实际应用. 近年, 氢气作为一种能源载体, 以其高能量密度和无碳排放的优点引起了人们的广泛关注, 被认为是缓解日益严重的污染问题的最有前途的环保能源. 对比目前采用的天然气热解和煤炭气化等传统制氢策略, 电催化水裂解由于催化效率高, 制氢纯度高和不产生温室气体, 被认为是高效、环保、可持续的制氢策略. 电催化水裂解由两个独立的半反应组成, 分别是析氢反应和析氧反应. 析氢反应作为水裂解的一个半反应, 在降低制氢成本及提高产氢催化效率方面起着关键作用. 然而, 目前的核心问题之一是要开发高效的析氢电催化剂, 以加快反应速度. 目前, 铂和铂基纳米材料被认为是高效的析氢电催化剂, 但是其稀缺性和高成本阻碍了大规模实际应用. 金属磷化物由于具有较高的本征活性并且在不同的电解质中都具有良好的电催化析氢性能, 被证明是一种优良的析氢电催化剂. 此外, 与普通催化剂相比, 金属磷化电催化剂还具有合成简便、效率高、成本低、省时等优点.
本文详细介绍了近年人们在金属磷化物用于电催化析氢研究中取得的进展. 首先, 介绍了电催化析氢反应机理, 金属磷化物的结构及作用, 并对其优缺点进行了总结; 随后, 综述了金属磷化物的合成方法, 包括后处理、原位生成和电沉积策略, 并对不同方法进行了比较和讨论. 此外, 从元素掺杂、界面工程、空穴工程、修饰特定载体、构建特定纳米结构、设计双或多金属磷化物和其他发展的新方法等七个方面详细总结了促进金属磷化物电催化活性的多种策略, 并进行了对比和讨论. 最后, 归纳了金属磷化物在电催化析氢应用中存在的问题和面临的挑战, 并对未来的研究发展提出了展望.

关键词: 金属磷化物, 电催化反应, 析氢反应, 合成策略, 氢能

Abstract:

Among the sustainable energy sources, hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels, as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting. The hydrogen evolution reaction (HER, a half-reaction of water splitting) plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes. Herein, we summarize the recent advances in the development of metal phosphides as HER electrocatalysts, focus on their synthesis (post-treatment, in situ generation, and electrodeposition methods) and the enhancement of their electrocatalytic activity (via elemental doping, interface and vacancy engineering, construction of specific supports and nanostructures, and the design of bi- or polymetallic phosphides), and highlight the crucial issues and challenges of future development.

Key words: Metal phosphides, Electrocatalytic reaction, Hydrogen evolution reaction, Synthesis strategies, Hydrogen energy

于文丽, 高玉肖, 陈智, 赵莹, 吴则星, 王磊. 优化金属磷化物电催化析氢性能的策略[J]. 催化学报, 2021, 42(11): 1876-1902.

Wenli Yu, Yuxiao Gao, Zhi Chen, Ying Zhao, Zexing Wu, Lei Wang. Strategies on improving the electrocatalytic hydrogen evolution performances of metal phosphides[J]. Chinese Journal of Catalysis, 2021, 42(11): 1876-1902.

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图/表 21

Fig. 1. Strategies on synthesizing and tuning the electrocatalytic HER performance of metal phosphides.

Fig. 2. Schematic strategies of metal phosphide synthesis.

Table 1 Comparison of metal phosphide electrocatalysts prepared using different methods.

Catalyst	P source	Electrolyte	η_{10 mA cm-2}/ mV	Tafel/ (mV dec^-1)	Ref.
Post-treatment methods
NiCu-P	red P	0.5 M H₂SO₄ 1 M PBS 1 M KOH	226 250 175	37 96 53	[84]
FLNPC@MoP-NC/MoP-C/CC	NaH₂PO₂	0.5 M H₂SO₄ 1 M PBS 1 M KOH	74 106 69	50 73 52	[85]
FeP/NCNSs	NaH₂PO₂	0.5 M H₂SO₄ 1 M PBS 1 M KOH	114 205 409	64 70 92	[86]
Ni₂P/Ni@C	NaH₂PO₂	0.5 M H₂SO₄	149	61	[87]
FeP film	NaH₂PO₂	0.5 M H₂SO₄ 1 M KOH	65 84	48.5 85	[88]
CoP/NPC/TF	NaH₂PO₂	0.5 M H₂SO₄ 1 M KOH	91 80	54 50	[89]
MoP@PC-CNTs	(NH₄)₂HPO₄	0.5 M H₂SO₄	220	55.9	[90]
MoP@PC	(NH₄)₂HPO₄	0.5 M H₂SO₄	258	59.3	[91]
Co/CoP@NC	NaH₂PO₂	0.5 M H₂SO₄ 1 M KOH	117 180	48.1 73.7	[92]
CoMn-P@NG	NaH₂PO₂	0.5 M H₂SO₄ 1 M KOH	140 164	110.69 64.85	[93]
MoP@PC/rGO	(NH₄)₂HPO₄	0.5 M H₂SO₄	62.3	53.6	[94]
In situ generation methods
N@MoPC_x-800	phenylphosphonic acid	0.5 M H₂SO₄ 1 M KOH	108 139	69.4 86.6	[95]
MoP@NPCS	hydroxyethylidene diphosphonic acid	1 M KOH	107	51	[96]
Ru-Ru₂P@NPC	saccharomycetes	0.5 M H₂SO₄ 1 M PBS 1 M KOH	42 41 46	39.75 56.79 39.75	[75]
Co-Co₂P@NPC/ rGO	saccharomycetes	0.5 M H₂SO₄	136	50.64	[74]
NiCo-NiCoP@ PCT/CC	phytic acid	1 M KOH	135	77.79	[97]
CoP-NB	phytic acid	0.5 M H₂SO₄	107	53	[98]
Electrodeposition methods
Co/CoP-NF	NaH₂PO₂	1 M NaOH	35	71	[81]
Co-P-S	NaH₂PO₂	1 M KOH	58	68	[82]
Ni-Mo-P/NF	NaH₂PO₂	1 M KOH	63	87.3	[76]
Ni_xP/NF	NaH₂PO₂	1 M KOH	63	55	[99]
Ni-P/NF	NaH₂PO₂	0.2 M KPi 1 M KOH	54 30	—	[79]
Co-Ni-P-2	NaH₂PO₂	1 M KOH	103	33	[80]
FeP nanocubes/CP	NaH₂PO₂	1 M KOH	140	61.92	[100]
Ni-Cu-P film	NaH₂PO₄· H₂O	0.5 M H₂SO₄ 1 M KOH	150 120	— 69	[83]

Fig. 3. Approaches used to improve the HER performance of metal phosphides.

Fig. 4. (a) Calculated free energy diagram for the HER on NiCoP and S-NiCoP. Reproduced with permission [111]. Copyright 2019, Royal Society of Chemistry. (b) Schematic fabrication of S-CoP. (c) Free energy diagram of HER on the (002) and (101) surfaces of CoP, CoP-S1, and S-CoP. (d) d-Orbital partial DOS of Co on the (002) surfaces of CoP, CoP-S1, and S-CoP. (e) Electron density map of the Co-H bonding region on the (002) surfaces of CoP, CoP-S1, and S-CoP. Red and blue denote the electron accumulation and depletion regions, respectively. (b?e) Reproduced with permission [113]. Copyright 2020, Royal Society of Chemistry. (f) Crystal structures of CoP2 and N-CoP2 with lattice constants and the corresponding mapping of orbital wave functions. Reproduced with permission [116]. Copyright 2020, American Association for the Advancement of Science. (g) HER polarization curves of Ni2P-based electrocatalysts in a neutral electrolyte. Reproduced with permission [118]. Copyright 2020, Elsevier.

Fig. 5. (a) Schematic formation of Ni-doped FeP/C hollow nanorods. (b) ΔGH* as a function of θH for Pt, FeP, and Ni-doped FeP. (a) and (b) Reproduced with permission [132]. Copyright 2019, American Association for the Advancement of Science. (c) Schematic energy bands of the individual water HOMO and the Co 3d orbital on the non-doped CoP (111) surface. (d) Schematic energy bands of the individual water HOMO and the M’ d-orbital on the M’-substituted CoP (111) surface. εF represents the Fermi level. (e) Calculated proportion of unoccupied d-orbitals (Pun) for different transition metal dopants. The Co atoms in CoP (111) are also treated as a dopant. The inset is the equation used to calculate Pun. (f) Electrochemical overpotential (η)@10 mA cm-2 for different transition-metal-doped CoP catalysts. (g) Trends in η@10 mA cm-2 for the alkaline HER as a function of Pun. (c?g) Reproduced with permission [137]. Copyright 2020, Cell Press.

Table 2 Comparison of metal phosphide electrocatalysts doped with different elements.

Catalyst	Dopant	Electrolyte	η_{10 mA cm-2}/ mV	Tafel (mV dec^-1)	Ref.
B-CoP/CNT	B	0.5 M H₂SO₄ 1 M PBS 1 M KOH	39 79 56	50 80 69	[140]
CoP-N/Co foam	N	1 M KOH	60	50.9	[141]
N-Ni₅P₄ hollow spheres	N	1 M KOH	96	62.2	[110]
N-MoP/CC	N	1 M KOH	70	55	[117]
H-NiCoP NWAs/NF	O	1 M KOH 1 M PBS	44 51	38.6 79.2	[108]
S-MoP NPL	S	0.5 M H₂SO₄ 1 M PBS 1 M KOH	86 142 104	34 98 56	[142]
S-NiCoP NW/CFP	S	1 M KOH	102	63.3	[111]
S-Ni₅P₄ NPA/CP	S	0.5 M H₂SO₄	56	43.6	[143]
S-CoP	S	1 M KOH	49	58.4	[113]
N,B-Ni₂P/G	N, B	0.5 M H₂SO₄ 1 M PBS 1 M KOH	79 124 92	48.3 60.4 57.7	[118]
Al-Ni₂P/TM	Al	1 M KOH	129	98	[121]
Fe-Co₂P BNRs	Fe	0.5 M H₂SO₄ 1 M KOH	159 156	95 90	[144]
Fe_0.074NiP	Fe	1 M KOH	108	52.1	[145]
Ni-FeP/TiN/CC	Ni	1 M KOH	75	73	[125]
Ni-WP₂ NSs/CC	Ni	0.5 M H₂SO₄	110	65	[146]
Mn-NiP₂/CC	Mn	0.5 M H₂SO₄ 1 M PBS 1 M KOH	69 107 97	45 91 61	[123]
0.05Mn-MoP	Mn	0.5 M H₂SO₄	199	49	[147]
V-Ni₂P NSAs/CC	V	1 M KOH	85	95	[148]
Co_0.9W_1.1P₂/C	W	0.5 M H₂SO₄ 1 M KOH	35 54	34 59	[149]
3% Bi/CoP	Bi	0.5 M H₂SO₄ 1 M KOH	150 122	64.5 60.2	[150]
V,N-CoP	V, N	0.5 M H₂SO₄ 1 M PBS 1 M KOH	81 146 57	59 88 54	[151]

Fig. 6. (a) Free energy diagram of H adsorption on the surfaces of NiSe2, Ni2P, and NiSe2-Ni2P. (b) H2O adsorption energies of Ni2P, NiSe2 and NiSe2-Ni2P. (a) and (b) Reproduced with permission [161]. Copyright 2019, Elsevier. (c) TEM image of P-MoP/Mo2N. Reproduced with permission [165]. Copyright 2020, Wiley-VCH. (d) Schematic synthesis of Ni-P/Ni/NF. Reproduced with permission [166]. Copyright 2019, Elsevier.

Fig. 7. (a) Schematic synthesis of CoP/CoMoP. Reproduced with permission [174]. Copyright 2019, Elsevier. (b) Linear sweep voltammograms of CFP, Cuf, NiP2-FeP2/CFP, NiP2-FeP2/CuNW/Cuf, and 20 wt% Pt/C/Cuf. Reproduced with permission [177]. Copyright 2020, American Chemical Society. (c) TEM image of P-Ni2P/Ru-1. (d) Linear sweep voltammograms of P-Ni2P/Ru-1 and the reference samples. Reproduced with permission [178]. Copyright 2020, Elsevier.

Table 3 Comparison of metal phosphide electrocatalysts with different interfaces.

Catalyst	Electrolyte	η_{10 mA cm-2}/ mV	Tafel (mV dec^-1)	Ref.
MoP/MoS₂-8	0.5 M H₂SO₄ 1 M PBS 1 M KOH	69 96 54	61 48 58	[164]
Ni₂P-NiSe₂/CC	1 M KOH	66	72.6	[162]
NiSe₂-Ni₂P/NF	1 M KOH	102	68	[161]
NiP₂/NiSe₂	1 M KOH	93	65.7	[179]
Ni-P/Ni/NF	0.5 M H₂SO₄ 0.1 M PBS 1 M KOH	83 112 129	68 179 70	[166]
Ni₂P/NiTe₂/NF	1 M KOH	62	80	[163]
Ni₂P-Ni₁₂P₅/NF	1 M KOH	76	68	[180]
Co₂P/CoMoP_x-0.4/NF	1 M NaOH	22	87.2	[173]
Co₂P/WC@NC	0.5 M H₂SO₄	91	40	[181]
CoMoP-5	0.5 M H₂SO₄ 0.1 M PBS 1 M KOH	95 89 110	61.1 96.5 64.1	[172]
CC@MoS₂/MoP/Ru-450	1 M KOH	45	52.9	[182]
CoP₃/Ni₂P	0.5 M H₂SO₄	115	49	[171]
CoP-MoO₂/MF	1 M KOH	42	127	[170]
CoP/NiCoP/NC	0.5 M H₂SO₄ 1 M PBS 1 M KOH	60 123 75	58 78 64	[176]
CoP-CeO₂/Ti	1 M KOH	43	54	[168]

Fig. 8. (a) Electron distribution map, with regions of electron accumulation and depletion indicated by yellow and cyan, respectively. (b) Two-dimensional charge difference isosurface, with regions of electron accumulation and depletion indicated by red and blue, respectively. (a) and (b) Reproduced with permission [194]. Copyright 2020, Wiley-VCH. (c) EPR spectra of NiCoP, Ar-NiCoP and Ar-NiCoP|V. Linear sweep voltammograms of the above catalysts for (d) HER and (e) OER tests. (c?e) Reproduced with permission [195]. Copyright 2019, Royal Society of Chemistry. (f) Free energy diagram and (g) density of states of FeP, Mg-FeP and Vc-FeP (111) surfaces. (f) and (g) Reproduced with permission [202]. Copyright 2017, Wiley-VCH.

Table 4 Comparison of metal phosphide electrocatalysts with different vacancies.

Catalyst	Vacancy parameter	Electrolyte	η_{10 mA cm-2}/ mV	Tafel (mV dec^-1)	Ref.
v-Ni₁₂P₅	P	1 M KOH	27.7	30.88	[194]
F-CoP-Vp-2	P	1 M PBS	108	88.9	[197]
Ar-NiCoP\|V	P	1 M KOH	58	51.7	[195]
D-Ni₅P₄\|Fe	P	1 M KOH	94.5	91	[204]
A-Ni₂P/Cu₃P	P	1 M KOH	88	89	[205]
Vc-FeP(NP)/Ti	Fe	1 M KOH	108	62	[202]
LC-WP	W	0.5 M H₂SO₄	170	52	[203]

Fig. 9. (a) ΔGH* values of CoP@DrGO, CoP@rGO, CoP, graphene, and Pt (111). Calculated differential charge density between P and H from top and side views of (b) CoP@DrGO and (c) CoP@rGO. (a?c) Reproduced with permission [212]. Copyright 2019, Elsevier. (d) SEM and (e) TEM images of MoP@NC-250. (f) H2O* (ΔEH2O*) and OH* (ΔEOH*) adsorption energies of selected Mo-containing catalysts. (g) Computed adsorption free energy profile of H2 evolution for different substrate surfaces. (d?g) Reproduced with permission [213]. Copyright 2020, Elsevier. (h) Schematic synthesis of CFC-CNT-CoOx/CoP. Reproduced with permission [216]. Copyright 2021, Elsevier.

Fig. 10. (a) Schematic synthesis of MCPS. Reproduced with permission [218]. Copyright 2019, American Chemical Society. Linear sweep voltammograms of the designed electrocatalysts in (b) 1 M KOH, (c) 0.5 M H2SO4, and (d) 1 M PBS. (b?d) Reproduced with permission [219]. Copyright 2020, Royal Society of Chemistry. (e) Cyclic voltammograms of CoP/C and CoP/CN/Ni in 1 M KOH. (f) Linear sweep voltammograms of Pt/C, CN/Ni, CoP/C, CoP/CN/Ni, and bare GC. Reproduced with permission [225]. Copyright 2021, Elsevier.

Table 5 Comparison of metal phosphide electrocatalysts with different supports.

Catalyst	Support	Electrolyte	η_{10 mA cm-2}/ mV	Tafel/ (mV dec^-1)	Ref.
CFC-CNT-CoO_x/CoP	CFC-CNT	1 M KOH	108	60	[216]
NiCoP-CNT@NiCo/ CP	CNT	1 M KOH	82	76	[226]
CoP-NC	NC	0.5 M H₂SO₄ 1 M PBS 1 M KOH	145 252 167	55 110 57	[227]
MoP@C	Mo,P co-doped carbon	1 M KOH	49	54	[228]
MoP@NC-250	NC	1 M KOH	96	53	[213]
Ni₁Co₃-P@CSs	CS	1 M KOH	57	44	[211]
MoP/CDs	CDs	1 M KOH	70	77.49	[206]
MCPS	MoS₂	0.5 M H₂SO₄ 1 M KOH	53 77	37 38	[218]
NiCoP/CoP-Ti₄O₇	Ti₄O₇	0.5 M H₂SO₄	128	65.5	[217]
Ni_2-_xMo_xP/NiMoO_4-_y	NiMoO_4-_y	1 M KOH	36	53	[229]
CoP/Ti₃C₂ MXene	Ti₃C₂ MXene	0.5 M H₂SO₄ 1 M PBS 1 M KOH	71 124 102	57.6 96.8 68.7	[219]
Ni₂P/Ti₃C₂T_x/NF	Ti₃C₂T_x	1 M KOH	135	86.6	[230]
CoP/CN/Ni	CN/Ni	0.5 M H₂SO₄ 1 M KOH	66 105	39.5 53.4	[225]

Fig. 11. (a) Schematic preparation of Co-Fe-P nanotubes. Reproduced with permission [236]. Copyright 2019, Elsevier. (b) SEM and (c) TEM images of 2D Co2P. (b,c) Reproduced with permission [241]. Copyright 2018, Royal Society of Chemistry. (d) Schematic synthesis of hollow FeP/C nanosheets. Reproduced with permission [243]. SEM images of pristine Ni(OH)2 (e) and the products obtained after the reaction with potassium hexacyanoferrate at 90 °C for 0.5 h (f), 2 h (g), 4 h (h), 8 h (i), 16 h (j), and 24 h (k). (e?k) Reproduced with permission [244]. Copyright 2018, Wiley-VCH.

Fig. 12. (a) Schematic synthesis of CoP@FeCoP/NC YSMPs. Reproduced with permission [253]. Copyright 2020, Elsevier. TEM images of (b) NiCoG-N, (c) NiCoG-80, (d) NiCoG-150, (e) NiCoG-220, and (f) schematic illustrations of the corresponding samples. (b?f) Reproduced with permission [261]. Copyright 2019, Elsevier. (g) Schematic synthesis of mesoporous metal phosphide microspheres. Reproduced with permission [262]. Copyright 2018, Royal Society of Chemistry.

Table 6 Comparison of metal phosphide electrocatalysts with different morphologies.

Catalyst	Morphology	Electrolyte	η_{10 mA cm-2}/mV	Tafel (mV dec^-1)	Ref.
Ni_xP-400	tripod	1 M KOH	71	79	[259]
HiHo-NiCoP	hollow-on-hollow	0.5 M H₂SO₄	103	52	[265]
CoP₂/CC	rhombic	0.5 M H₂SO₄ 1 M KOH	56 72	67 88	[258]
3DN-Ni₂P-Ni	3D nanopatterning	0.5 M H₂SO₄	101	60	[266]
CoP-based microspheres	microsphere	0.5 M H₂SO₄ 1 M KOH	125 121	— —	[262]
HWS-NiCoP/NF-A30	whisker-on-sheet	1 M KOH	42	66	[267]
np-CoP₃/TM	nanowire	1 M KOH	76	45	[268]
Ni_1.8Cu_0.2-P/NF	holey nanosheets	1 M KOH	78	70	[269]
CoNiP microspheres	multi-shelled hollow microsphere	1 M KOH	145.8	52	[270]
Ni₂P-NW	nanowire	0.5 M H₂SO₄ 0.5 M PBS 0.11 M KOH	89 108 139	59 — —	[271]
Ni₂P/CF-30	array	0.5 M H₂SO₄	63	67	[272]
CoNiP-4	nanobox	1 M KOH	138	65	[273]
Co-P@IC/(Co-Fe)P@CC	nanocube	1 M KOH	53	88	[274]
Ni₂P@NSG	0D nanocrystal	1 M KOH	110	43	[275]

Fig. 13. (a) Linear sweep voltammograms of NCPs in 1 M KOH. Reproduced with permission [278]. Copyright 2019, American Chemical Society. (b) Linear sweep voltammograms of Ni2P, FexNi2-xP, and FeP in 0.5 M H2SO4. (c) Exchange current densities and the overpotentials@50 mA cm-2 of Ni2P (wine red), Fe0.5Ni1.5P (red), Fe1.0Ni1.0P (orange), Fe1.5Ni0.5P (green), and Fe2P (blue). Reproduced with permission [280]. Copyright 2020, American Chemical Society. (d) Calculated ΔGH* of CNF-supported Ru/Fe phosphide electrocatalysts. Reproduced with permission [204]. Copyright 2020, Elsevier. (e) Calculated ΔGH* of MoxCo1-xP catalysts. Reproduced with permission [282]. Copyright 2019, Royal Society of Chemistry. (f) Linear sweep voltammograms of FeCoCuP@NC, FeCuP@NC, FeCoP@NC, FeP@NC, CoCuP@NC, CoP@NC, and CuP@NC. Reproduced with permission [283]. Copyright 2020, Elsevier.

Table 7 Comparison of bi- and polymetallic phosphides as HER catalysts.

Catalyst	Element	Electrolyte	η_{10 mA cm}^-2/ mV	Tafel/ mV dec^-1	Ref.
MoNiP	Mo,Ni	0.5 M H₂SO₄	134	66	[290]
NiCoP hollow polyhedron	Ni, Co	0.5 M H₂SO₄	82	72	[291]
CoNiP/Co_xP	Co,Ni	1 M PBS 1 M KOH Natural seawater	117 36 290	— 70 —	[292]
FeCoP₂@NPPC	Fe, Co	0.5 M H₂SO₄ 1 M KOH	114 150	79 79	[293]
Ni₁-Co₁-P	Ni,Co	1 M KOH	90	60.2	[294]
CoNiP-1:1 NWs	Co,Ni	1 M KOH	252	128	[295]
Ni₁₂P₅-Ni₄Nb₅P₄/ PCC	Ni,Nb	1 M KOH	81	64	[296]
NiCo_xP_y-P/CC	Ni,Co	0.5 M H₂SO₄ 1 M KOH	70 42	61 66	[297]
Fe₁-NiCoP	Fe,Co,	1 M KOH	60	51.1	[298]
CC-NC-NiFeP	Ni,Fe	1 M KOH	94	70	[299]
Ni₂P / MoP-CC	Ni, Mo	1 M KOH	64	78	[300]
FeCoCuP@NC	Fe,Co,Cu	0.5 M H₂SO₄ 1 M KOH	80 169	47.6 48.8	[283]
FeCoNiP@NC	Fe,Co,Ni	0.5 M H₂SO₄ 1 M KOH	93 187	51.7 52.2	[301]
np-NiFeMoP	Ni,Fe,Mo	1 M KOH	223	180.3	[302]

Fig. 14. (a) HER activities of MoP700, MoP2, MoP, Mo3P, and Pt/C in acidic, neutral, and basic solutions. (b) Schematic illustration of MoP700-promoted HER at neutral pH. (a) and (b) Reproduced with permission [306]. Copyright 2019, American Chemical Society. (c) Images of H2 bubbles on blank NF and Ni2P/NF together with a schematic illustration of the adhesion behavior of these bubbles on the above materials. Reproduced with permission [307]. Copyright 2019, American Chemical Society. (d) Schematic synthesis of CoP/Co-MOF/CF. Reproduced with permission [308]. Copyright 2019, Wiley-VCH. (e) Linear sweep voltammograms of CoP2 NCs, CoP NCs, Co2P NCs, and Pt/C in 0.5 M H2SO4. Reproduced with permission [310]. Copyright 2019, Wiley-VCH.

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优化金属磷化物电催化析氢性能的策略

Strategies on improving the electrocatalytic hydrogen evolution performances of metal phosphides

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