过渡金属磷化物基材料在电催化析氢中的改性策略：现状及展望

雷琬莹; 吴攀; 司渭滨; 赵亮; 谭自强; 杨鑫鑫; 乔明涛; 张婷婷

doi:10.13801/j.cnki.fhclxb.20231120.002

过渡金属磷化物基材料在电催化析氢中的改性策略：现状及展望

doi: 10.13801/j.cnki.fhclxb.20231120.002

1.
西安建筑科技大学　材料科学与工程学院，西安 710055
2.
定西市产品质量监督检验所，定西 743000

基金项目: 国家自然科学基金(51902443)；陕西省教育厅重点研究项目(22JY039；22JY037)

详细信息

通讯作者:
雷琬莹，博士，副教授，硕士生导师，研究方向为纳米复合材料、能源转化与利用　E-mail: leiwy@xauat.edu.cn

中图分类号: TB331
计量
- 文章访问数: 286
- HTML全文浏览量: 377
- PDF下载量: 40
- 被引次数: 0
出版历程
- 收稿日期: 2023-09-05
- 修回日期: 2023-11-03
- 录用日期: 2023-11-09
- 网络出版日期: 2023-11-21
- 刊出日期: 2024-04-15

Modification strategies of transition metal phosphide-based materials in electrocatalytic hydrogen evolution: Current status and prospect

1.
College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China
2.
Dingxi, Products Quality Supervision and Inspection Institute, Dingxi 743000, China

Funds: National Natural Science Foundation of China (51902443); Key Research Project of Shaanxi Education Department (22JY039; 22JY037)

摘要

摘要: 氢能作为一种零碳燃料，被认为是替代化石能源的理想能源。电催化析氢(HER)是一种绿色环保技术，可以裂解水分子制备氢气。因此开发低廉高效且稳定性好的非贵金属催化剂对于解决能源危机和可持续发展尤为重要。过渡金属磷化物(TMPs)具有良好的导电性、多变的化学组成、丰富的储量和稳定的理化性质，是HER反应重要的催化剂之一。本文首先介绍了HER反应机制及TMPs的结构特点，然后总结了TMPs的合成方法包括液相合成法和气-固合成法等，接着重点分析了现有TMPs的改性策略如形貌调控、缺陷调控、元素掺杂和界面复合，最后对未来TMPs的发展方向提出了展望。
- 过渡金属磷化物 /
- 氢能 /
- 电催化 /
- 析氢反应 /
- 改性策略
Abstract: Hydrogen, a zero-carbon fuel, is supposed to be the potential alternative for fossil energy. Electrocatalytic hydrogen evolution reaction (HER) is a green technology that could split water molecules to produce hydrogen. Therefore, exploring the low-cost, efficient and long-stable noble metal-free catalysts is particularly important for solving the problems of energy crisis and sustainable development. Transition metal phosphides (TMPs) possess excellent electrical conductivity, variable chemical composition, abundant reserves and stable physicochemical properties, which is one of the critical catalysts in HER. Herein, the HER mechanism and the structural characteristics of TMPs are introduced at first, then the fabrication approaches of TMPs like liquid phase formation, gas-solid synthesis, etc. are summarized. This paper are mainly focusing on the recent modification strategies for TMPs-based nanostructures, such as morphology regulation, vacancy creation, elemental doping and interface engineering. Finally, the future directions for the development of TMPs is proposed.
- transition metal phosphide /
- hydrogen /
- electrocatalysis /
- hydrogen evolution reaction /
- modification strategies

HTML全文

图 1 电催化析氢(HER)反应机制图

Figure 1. Diagram of the electrocatalytic hydrogen evolution reaction (HER) reaction mechanism

下载: 全尺寸图片幻灯片

图 2 过渡金属磷化物(TMPs)的晶胞示意图

Figure 2. Schemtaic of the unit cell for transition metal phosphides (TMPs)

P—Phosphorus; M—Metal

下载: 全尺寸图片幻灯片

图 3 NiP-Pt/Co(OH)₂ (a)^[30]和CoFeP/还原氧化石墨烯(rGO) (b)的合成过程示意图^[32]

Figure 3. Schematic illustration of the synthesis process of NiP-Pt/Co(OH)₂ (a)^[30] and CoFeP/reduced graphene oxide (rGO) (b)^[32]

GO—Graphene oxide; LDH—Layered double hydroxides

下载: 全尺寸图片幻灯片

图 4 Fe-CoP (a)^[39]和3D WP₂ 纳米线 (b)^[42]的SEM图像；(c) FeP、Mg-FeP和Vc-FeP的(111)晶面的结合能图^[43]；(d) CoP的线性扫描伏安曲线^[44]

Figure 4. SEM images of Fe-CoP (a)^[39]and 3D WP₂ nanowire (b)^[42]; (c) Free energy diagram of FeP, Mg-FeP and Vc-FeP of (111) crystal plane^[43]; (d) Liner sweep voltammetry curves of CoP^[44]

Vc-FeP—Fe-vacancy-rich FeP; F-CoP-Vp—F doping and P vacancies CoP; U—Voltage; RHE—Reversible hydrogen electrode

下载: 全尺寸图片幻灯片

图 5 (a) W-NiCoP/镍泡沫(NF)的HER机制图^[49]；(b) Cu-CoP材料不同位点的HER反应能垒图^[50]；(c) H和金属位之间态密度图^[51]；(d) 恒电位下C-Co₂P的原位拉曼光谱及等值线图^[72]

Figure 5. (a) HER mechanism for W-NiCoP/nickel foam (NF)^[49]; (b) HER free energy diagrams for various sites on Cu-CoP^[50]; (c) Partial density of states between H and active metallic site^[51]; (d) In-situ Raman spectra and corresponding contour plots of C-Co₂P at constant potentials^[72]

OCP—Open circuit potential; DOS—Density of states

下载: 全尺寸图片幻灯片

图 6 CoP₃/Fe₂P@NF (a)^[23]和CoP-WP/rGO (b)^[77]的HRTEM图像；(c) CoP₃/Fe₂P@NF的线性扫描伏安曲线^[23]；(d) CoP-WP/rGO的结合能图^[77]

Figure 6. HRTEM images of CoP₃/Fe₂P@NF (a)^[23] and CoP-WP/rGO (b)^[77]; (c) Liner sweep voltammetry curves of CoP₃/Fe₂P@NF^[23];(d) Free-energy diagram of CoP-WP/rGO^[77]

下载: 全尺寸图片幻灯片

表 1 通过缺陷调控改善TMPs 基电催化剂的HER性能的总结

Table 1. Summary of the HER performance for TMPs-based electrocatalysts by vacancy creation

Catalyst	Vacancy	Substrate	Current density/ (mA·cm⁻²)	Overpotential/ mV	Tafel slope/ (mV·dec⁻¹)	Ref.
WP	Cationic vacancies	Glassy carbon electrode	100	175	58	[18]
Vc-FeP	Cationic vacancy	Ti foils	10	108	33	[43]
F-CoP-Vp	Anion vacancies	Carbon fiber cloth	10	108	88.9	[44]
V-Ni₂P/NF	Cationic vacancy	Nickel foam (NF)	10	81	48	[45]
WP	Cationic vacancies	Glassy carbon electrode	300	80.6	52	[46]
S-CoP-p	P vacancies	Ti mesh	100	114	58.4	[47]

下载: 导出CSV

表 2 通过元素掺杂改善TMPs 基电催化剂的HER性能的总结

Table 2. Summary of the HER performance for TMPs-based electrocatalysts by elemental doping

Catalyst	Substrate	Current density/(mA·cm⁻²)	Overpotential/mV	Tafel slope/(mV·dec⁻¹)	Ref.
MnCoP/CC	Carbon cloth (CC)	10	65	46.16	[29]
Fe-CoP@CC	Carbon cloth	10	49	149	[39]
W-NiCoP/NF	Nickel foam (NF)	10	29.6	38	[49]
Cu-CoP NAs/CP	Carbon paper (CP)	10	81	83.5	[50]
S-WP₂	Carbon cloth	10	115	75	[51]
Zn/F-NiCoP/NF	Nickel foam	10	59	81.03	[52]
V-Co_xP@NC	Carbon paper	10	106	93	[53]
Mn-CoP	Glassy carbon electrode	10	148	61	[54]
CoP-N/Co foam	Co foam	50	100	50.9	[55]
W, Ru-NiP₂	Nickel foam	10	17.8	67.5	[56]
F_0.25CP-G	Graphene (G)	10	66	61	[57]
O-CoP	Glassy carbon electrode	10	98	59.9	[58]
Mo-CoFeP/NC	Glassy carbon electrode	10	145	68	[59]
pCoMo-P/ NF	Nickel foam	10	49	55.02	[60]
O-CoP	Glassy carbon electrode	10	116	59	[61]
Mn-doped CoP/NF	Nickel foam	10	60	56.7	[62]
V-Ni₅P₄	Nickel foam	10	13	—	[63]
Co-Cu₃P/CF	Cu foam (CF)	100	250	75	[64]
CoFeP/C	Graphene	10	42.1	59	[65]
V-CoP/CC	Carbon cloth	10	71	67.6	[66]
Mn-CoP PMFs/CC	Carbon cloth	10	90	86.1	[67]
V-doped CoP/NF	Nickel foam	10	84.6	79.2	[68]
CoFeP/NF	Nickel foam	10	29.8	68.4	[69]
Ga-CoP NSs/CFP	Carbon fiber paper (CFP)	10	44	62	[70]
Nb-CoP	Glassy carbon electrode	10	99	59.4	[71]
Notes: NAs—Nanosheet arrays; PMFs—Peony-like micro-flower; NSs—Nanosheets; NC—Nitrogen doped carbon.

下载: 导出CSV

表 3 界面复合调控TMPs 基电催化剂的HER性能的总结

Table 3. Summary of the HER performance for TMPs-based catalysts by interface engineering

Catalyst	Substrate	Current density/(mA·cm⁻²)	Overpotential/mV	Tafel slope/(mV·dec⁻¹)	Ref.
NiCoP@FeP_x	–	10	82.5	69.1	[17]
CoP₃/Fe₂P@NF	Nickel foam	10	81	104.4	[23]
Co₂P&CoP@NC	Nickel foam	10	62.8	60	[33]
NiP-Pt/Co(OH)₂	Nickel foam	10	40	49.85	[30]
CoFeP/rGO	Glassy carbon electrode	10	101	169	[32]
CoFeP NS@Fe-CoP	Nickel foam	10	78	73	[73]
NiFe LDH/CoFeP/NF	Nickel foam	50	198	75.2	[74]
CoP/NiCoP	N-doped carbon	10	75	64	[75]
Cu₃P/NiCoP	Nickel-cobalt foam	10	51	89	[76]
CoP-WP/rGO	Nickel foam	10	138	62	[77]
g-C₃N₄/Cu₃P	Cu foil	10	67	45	[78]
W₂C/WP@NC	Glassy carbon electrode	10	116.37	59.07	[79]
NiP/Wood	Pristine wood	10	83	73.2	[80]
Cu₃P@NPC	Copper foam	10	81.94	81.25	[81]
CoFeP NFs/NPCNT	Glassy carbon electrode	10	132	62.9	[82]
CoP/Mo₂CT_x	Glassy carbon electrode	10	78	66	[83]
N-CoO@CoP	Nickel foam	100	201	37	[84]
Fe₂O₃-TiO₂/rGO	Reduced graphene oxide	10	96	98	[85]
Ni₂P@NPCNFs	Carbon cloth	10	63.2	56.7	[86]
CoFeP NS@NCNF	Nickel foam	10	113	108	[87]
CoFeOH/CoFeP/IF	Iron foam (IF)	100	114.9	128.37	[88]
Notes: NPC—Nitrogen and phosphorus co-doped carbon; NPCNT—Nitrogen and phosphorus co-doped carbon nanotubes; NPCNFs—Nitrogen-doped porous carbon nanofibers; NCNF—Nitrogen-doped carbon nanofiber; NFs—Nanoframes; MoCT—Molybdenum carbide (T is the surface terminal group).

下载: 导出CSV

参考文献(88)

[1]	GUO X, LI M G, QIU L Y, et al. Engineering electron redistribution of bimetallic phosphates with CeO₂ enables high-performance overall water splitting[J]. Chemical Engineering Journal, 2023, 453: 139796. doi: 10.1016/j.cej.2022.139796
[2]	SHAN A X, TENG X A, ZHANG Y, et al. Interfacial electronic structure modulation of Pt-MoS₂ heterostructure for enhancing electrocatalytic hydrogen evolution reaction[J]. Nano Energy, 2022, 94: 106913. doi: 10.1016/j.nanoen.2021.106913
[3]	WANG C S, ZHANG Q, YAN B, et al. Facet engineering of advanced electrocatalysts toward hydrogen/oxygen evolution reactions[J]. Nano-Micro Letters, 2023, 15: 52. doi: 10.1007/s40820-023-01024-6
[4]	WANG L, GONG N, ZHOU Z, et al. Electronic modulation of multi-element transition metal phosphide by V-doping for high-efficiency and pH-universal hydrogen evolution reactio[J]. International Journal of Hydrogen Energy, 2022, 47: 18305-18313. doi: 10.1016/j.ijhydene.2022.04.024
[5]	CHEN Z J, DUAN X G, WEI W, et al. Recent advances in transition metal-based electrocatalysts for alkaline hydrogen evolution[J]. Journal of Materials Chemistry A, 2019, 7: 14971-15005. doi: 10.1039/C9TA03220G
[6]	WANG J J, YUE X Y, YANG Y Y, et al. Earth-abundant transition-metal-based bifunctional catalysts for overall electrochemical water splitting: A review[J]. Journal of Alloys and Compounds, 2020, 819: 153346. doi: 10.1016/j.jallcom.2019.153346
[7]	姜金池, 金彪, 孟龙月. 基于电催化析氧反应的非贵金属催化剂研究进展[J]. 复合材料学报, 2023, 40(3): 1365-1380. doi: 10.13801/j.cnki.fhclxb.20220819.001 JIANG Jinchi, JIN Biao, MENG Longyue. Research progress of non-noble metal catalysts based on electrocatalytic oxygen evolution reaction[J]. Acta Materiae Compositae Sinica, 2023, 40(3): 1365-1380(in Chinese). doi: 10.13801/j.cnki.fhclxb.20220819.001
[8]	GAO Y Y, QIAN S, WANG H J, et al. Boron-doping on the surface mediated low-valence Co centers in cobalt phosphide for improved electrocatalytic hydrogen evolution[J]. Applied Catalysis B-Environmental, 2023, 320: 122014. doi: 10.1016/j.apcatb.2022.122014
[9]	姚素薇, 李贺, 张卫国, 等. AC/Ni-Co复合电极材料的制备及其催化析氢性能[J]. 复合材料学报, 2006, 23(3): 77-81. YAO Suwei, LI He, ZHANG Weiguo, et al. Preparation and property for hydrogen evolution of AC (activated char)/Ni-Co composite electrode materials[J]. Acta Materiae Compositae Sinica, 2006, 23(3): 77-81(in Chinese).
[10]	YANG S F, YANG X B, WANG Q, et al. Facet-selective hydrogen evolution on Rh₂P electrocatalysts in pH-universal media[J]. Chemical Engineering Journal, 2022, 449: 137790. doi: 10.1016/j.cej.2022.137790
[11]	DU H T, KONG R M, GUO X X, et al. Recent progress in transition metal phosphides with enhanced electrocatalysis for hydrogen evolution[J]. Nanoscale, 2018, 10: 21617-21624. doi: 10.1039/C8NR07891B
[12]	LI W F, JIANG Y, LI Y R, et al. Electronic modulation of CoP nanoarrays by Cr-doping for efficient overall water splitting[J]. Chemical Engineering Journal, 2021, 425: 130651. doi: 10.1016/j.cej.2021.130651
[13]	LIN Y, CHEN X M, TUO Y X, et al. In-situ doping-induced lattice strain of NiCoP/S nanocrystals for robust wide pH hydrogen evolution electrocatalysis and supercapacitor[J]. Journal of Energy Chemistry, 2022, 70: 27-35. doi: 10.1016/j.jechem.2022.02.024
[14]	李创, 王宇, 候利强, 等. 多孔碳负载钌单原子和钌纳米团簇催化剂用于高效析氢反应[J]. 复合材料学报, 2023, 40(4): 2155-2168. LI Chuang, WANG Yu, HOU Liqiang, et al. Porous carbon supported ruthenium single atom and ruthenium nanoclusters catalysts for efficient hydrogen evolution reaction[J]. Acta Materiae Compositae Sinica, 2023, 40(4): 2155-2168(in Chinese).
[15]	GUO Z T, LIU L, WANG J Q, et al. Recent progress in CoP-based materials for electrochemical water splitting[J]. International Journal of Hydrogen Energy, 2021, 46(69): 34194-34215.
[16]	ZHANG X D, KIM S, GUO X Y, et al. Impacts of boron doping on the atomic structure, stability, and photocatalytic activity of Cu₃P nanocrystals[J]. Applied Catalysis B: Environmental, 2021, 298: 120515.
[17]	LI M X, LIU X X, HU X L, et al. Fabrication of core-sheath NiCoP@FeP_x nanoarrays for efficient electrocatalytic hydrogen evolution[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(7): 8847-8855.
[18]	LI F, WANG C R, HAN X C, et al. Confinement effect of mesopores: In situ synthesis of cationic tungsten-vacancies for a highly ordered mesoporous tungsten phosphide electrocatalyst[J]. ACS Applied Materials & Interfaces, 2020, 12(20): 22741-22750.
[19]	XIONG L W, QIU Y F, ENG X, et al. Electronic structural engineering of transition metal-based electrocatalysts for the hydrogen evolution reaction[J]. Nano Energy, 2022, 104: 107882. doi: 10.1016/j.nanoen.2022.107882
[20]	ZHAGN X Y, XIE J Y, MA Y, et al. An overview of the active sites in transition metal electrocatalysts and their practical activity for hydrogen evolution reaction[J]. Chemical Engineering Journal, 2022, 430: 132312. doi: 10.1016/j.cej.2021.132312
[21]	ZHU C R, GAO D Q, DING J, et al. TMD-based highly efficient electrocatalysts developed by combined computational and experimental approaches[J]. Chemical Society Reviews, 2018, 47: 4332-4356. doi: 10.1039/C7CS00705A
[22]	FENG S Y, YU Y H, LI J, et al. Recent progress in seawater electrolysis for hydrogen evolution by transition metal phosphides[J]. Catalysis Communications, 2022, 162: 106382. doi: 10.1016/j.catcom.2021.106382
[23]	YANG Y Y, YANG J Y, KONG C, et al. Heterogeneous cobalt-iron phosphide nanosheets formed by in situ phosphating of hydroxide for efficient overall water splitting[J]. Journal of Alloys and Compounds, 2022, 926: 166930. doi: 10.1016/j.jallcom.2022.166930
[24]	HONG L F, GUO R T, YUAN Y, et al. Recent progress of transition metal phosphides for photocatalytic hydrogen evolution[J]. ChemSusChem, 2021, 14(2): 539-557.
[25]	OYAMA S T, GOTT T, ZHAO H, et al. Transition metal phosphide hydroprocessing catalysts: A review[J]. Catalysis Today, 2009, 143: 94-107. doi: 10.1016/j.cattod.2008.09.019
[26]	JI L L, WANG J Y, TENG X, et al. CoP nanoframes as bifunctional electrocatalysts for efficient overall water splitting[J]. ACS Catalysis, 2020, 10(1): 412-419 . doi: 10.1021/acscatal.9b03623
[27]	SU J Z, ZHOU J L, WANG L, et al. Synthesis and application of transition metal phosphides as electrocatalyst for water splitting[J]. Science Bulletin, 2017, 62: 633-644. doi: 10.1016/j.scib.2016.12.011
[28]	YANG X L, LU A Y, ZHU Y H, et al. CoP nanosheet assembly grown on carbon cloth: A highly efficient electrocatalyst for hydrogen generation[J]. Nano Energy, 2015, 15: 634-641. doi: 10.1016/j.nanoen.2015.05.026
[29]	WANG M S, FU W Y, DU L, et al. Surface engineering by doping manganese into cobalt phosphide towards highly efficient bifunctional HER and OER electrocatalysis[J]. Applied Surface Science, 2020, 515: 146059. doi: 10.1016/j.apsusc.2020.146059
[30]	LIU Z X, GUO Z G, HE H L, et al. Interface regulation of Pt quantum dots doped nickel phosphide and cobalt hydroxide to promote electrocatalytic overall water splitting[J]. International Journal of Hydrogen Energy, 2022, 47: 40986-40998. doi: 10.1016/j.ijhydene.2022.09.182
[31]	ZONG Q, LIU C F, YANG H, et al. Tailoring nanostructured transition metal phosphides for high-performance hybrid supercapacitors[J]. Nano Today, 2021, 38: 101201. doi: 10.1016/j.nantod.2021.101201
[32]	CAI X D, SONG Q, JIAO D H, et al. Bifunctional electrocatalysts of CoFeP/rGO heterostructure for water splitting[J]. International Journal of Hydrogen Energy, 2022, 47: 39499-39508. doi: 10.1016/j.ijhydene.2022.09.112
[33]	YI X L, SONG L Z, OUYANG S X, et al. Structural and componential engineering of Co₂P&CoP@N-C nanoarrays for energy-efficient hydrogen production from water electrolysis[J]. ACS Applied Materials & Interfaces, 2021, 13(47): 56064-56072 .
[34]	PU Z H, LIU T T, AMIINU I S, et al. Transition-metal phosphides: Activity origin, energy-related electrocatalysis applications, and synthetic strategies[J]. Advanced Functional Materials, 2020, 30(45): 2004009.
[35]	WU J J, FU Z W. Pulsed-laser-deposited Sn₄P₃ electrodes for lithium-ion batteries[J]. Journal of the Electrochemical Society, 2009, 156: A22. doi: 10.1149/1.3005960
[36]	YU F, ZHOU H Q, HUANG Y F, et al. High-performance bifunctional porous non-noble metal phosphide catalyst for overall water splitting[J]. Nature Communications, 2018, 9: 2551. doi: 10.1038/s41467-018-04746-z
[37]	LU X F, YU L, LOU X W. Highly crystalline Ni-doped FeP/carbon hollow nanorods as all-pH efficient and durable hydrogen evolving electrocatalysts[J]. Science Advances, 2019, 5(2): eaav6009.
[38]	ZHAO X J, LUO D, WANG Y, et al. Reduced graphene oxide-supported CoP nanocrystals confined in porous nitrogen-doped carbon nanowire for highly enhanced lithium/sodium storage and hydrogen evolution reaction[J]. Nano Research, 2019, 12: 2872-2880. doi: 10.1007/s12274-019-2529-y
[39]	YANG Y Y, MENG H X, KONG C, et al. Template-free synthesis of 1D hollow Fe doped CoP nanoneedles as highly activity electrocatalysts for overall water splitting[J]. International Journal of Hydrogen Energy, 2021, 46: 28053-28063. doi: 10.1016/j.ijhydene.2021.06.047
[40]	ZHAO L, WEN M, TIAN Y K, et al. A novel structure of quasi-monolayered NiCo-bimetal-phosphide for superior electrochemical performance[J]. Journal of Energy Chemistry, 2022, 74: 203-211. doi: 10.1016/j.jechem.2022.07.017
[41]	TIAN Y S, LI S Y, QIN P P, et al. Metal-organic frameworks derived multidimensional CoP/N, P-doped carbon architecture as an efficient electrocatalyst for overall water splitting[J]. ChemCatChem, 2021, 13(13): 3037-3045. doi: 10.1002/cctc.202100272
[42]	MENG F Y, YU Y, SUN D F, et al. Three-dimensional flower-like WP₂ nanowire arrays grown on Ni foam for full water splitting[J]. Applied Surface Science, 2021, 546: 148926. doi: 10.1016/j.apsusc.2021.148926
[43]	KWONG W L, GRACIA-ESPINO E, LEE C C, et al. Cationic vacancy defects in iron phosphide: A promising route toward efficient and stable hydrogen evolution by electrochemical water splitting[J]. ChemSusChem, 2017, 10(22), 4544-4551.
[44]	XU K, SUN Y Q, LI X L, et al. Fluorine-induced dual defects in cobalt phosphide nanosheets enhance hydrogen evolution reaction activity[J]. ACS Materials Letters, 2020, 2(7): 736-743.
[45]	ZHANG W Z, CHEN G Y, ZHAO J, et al. Self-growth Ni₂P nanosheet arrays with cationic vacancy defects as a highly efficient bifunctional electrocatalyst for overall water splitting[J]. Journal of Colloid and Interface Science, 2020, 561: 638-646. doi: 10.1016/j.jcis.2019.11.039
[46]	ZHANG X Y, GUO T, LIU T Y, et al. Tungsten phosphide (WP) nanoparticles with tunable crystallinity, W vacancies, and electronic structures for hydrogen production[J]. Electrochimica Acta, 2019, 323: 134798. doi: 10.1016/j.electacta.2019.134798
[47]	XU R R, JIANG T F, FU Z, et al. Ion-exchange controlled surface engineering of cobalt phosphide nanowires for enhanced hydrogen evolution[J]. Nano Energy, 2020, 78: 105347. doi: 10.1016/j.nanoen.2020.105347
[48]	孙兴伟, 白杰, 李春萍, 等. 钴基电极材料的改性策略及其应用研究[J]. 复合材料学报, 2023, 40(5): 2550-2565. SUN Xingwei, BAI Jie, LI Chunping, et al. Modification strategy and application of cobalt-based electrode materials[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2550-2565(in Chinese).
[49]	LU S S, ZHANG L M, DONG Y W, et al. Tungsten-doped Ni-Co phosphides with multiple catalytic sites as efficient electrocatalysts for overall water splitting[J]. Journal of Materials Chemistry A, 2019, 7(28): 16859-16866. doi: 10.1039/C9TA03944A
[50]	YAN L, ZHANG B, ZHU J L, et al. Electronic modulation of cobalt phosphide nanosheet arrays via copper doping for highly efficient neutral-pH overall water splitting[J]. Applied Catalysis B: Environmental, 2020, 265: 118555. doi: 10.1016/j.apcatb.2019.118555
[51]	LIU W, XIAO Z Z, CHANDRASEKARAN S, et al. Insights into the effect of sulfur incorporation into tungsten diphosphide for improved hydrogen evolution reaction[J]. ACS Applied Materials & Interfaces, 2022, 14(14): 16157-16164.
[52]	ZHU J J, ZHENG X Y, LIU C C, et al. Zinc and fluorine ions dual-modulated NiCoP nanoprism array electrocatalysts for efficient water splitting[J]. Journal of Colloid and Interface Science, 2023, 630: 559-569. doi: 10.1016/j.jcis.2022.10.136
[53]	GUO W H, ZHANG Q, WANG X H, et al. MOF-derived V-Co_xP@NC nanoarchitectures for highly enhanced electrocatalytic water splitting through electronical tuning[J]. Electrochimica Acta, 2020, 357: 136850. doi: 10.1016/j.electacta.2020.136850
[54]	LI Y L, JIA B M, CHEN B Y, et al. MOF-derived Mn doped porous CoP nanosheets as efficient and stable bifunctional electrocatalysts for water splitting[J]. Dalton Transactions, 2018, 47: 14679-14685. doi: 10.1039/C8DT02706D
[55]	LIU Z, YU X, XUE H G, et al. A nitrogen-doped CoP nanoarray over 3D porous Co foam as an efficient bifunctional electrocatalyst for overall water splitting[J]. Journal of Materials Chemistry A, 2019, 7(21): 13242-13248. doi: 10.1039/C9TA03201K
[56]	QIN L, SONG T S, GUO L, et al. Boosting the electrocatalytic performance of ultrathin NiP₂ nanosheets by synergic effect of W and Ru doping engineering[J]. Applied Surface Science, 2020, 508: 145302. doi: 10.1016/j.apsusc.2020.145302
[57]	TAHMASEBI Z, MOHAMMADI ZARDKHOSHOUI A, HOSSEINY DAVARANI S S. Facile synthesis of Fe-doped CoP nanosheet arrays wrapped by graphene for overall water splitting[J]. Dalton Transactions, 2021, 50(35): 12168-12178.
[58]	ZHOU G Y, LI M, LI Y L, et al. Regulating the electronic structure of CoP nanosheets by O incorporation for high-efficiency electrochemical overall water splitting[J]. Advanced Functional Materials, 2020, 30(7): 1905252.
[59]	FU R R, JIAO X G, YU J A, et al. Mo-doped CoFeP/nitrogen doped carbon porous nanocubes for alkaline hydrogen production[J]. Journal of Electroanalytical Chemistry, 2023, 930: 117137. doi: 10.1016/j.jelechem.2022.117137
[60]	HAN Y C, LI P F, TIAN Z F, et al. Molybdenum-doped porous cobalt phosphide nanosheets for efficient alkaline hydrogen evolution[J]. ACS Applied Energy Materials, 2019, 2(9): 6302-6310. doi: 10.1021/acsaem.9b00924
[61]	MA Y, ZHOU G Y, LIU Z Y, et al. Electronic structural regulation of CoP nanorods by the tunable incorporation of oxygen for enhanced electrocatalytic activity during the hydrogen evolution reaction[J]. Nanoscale, 2020, 12(27): 14733-14738. doi: 10.1039/D0NR03685D
[62]	MENG C, WANG Z M, ZHANG L J, et al. Tuning the Mn dopant to boost the hydrogen evolution performance of CoP nanowire arrays[J]. Inorganic Chemistry Frontiers, 2022, 61(25): 9832-9839.
[63]	RAO Y, WANG S W, ZHANG R Y, et al. Nanoporous V-doped Ni₅P₄ microsphere: A highly efficient electrocatalyst for hydrogen evolution reaction at all pH[J]. ACS Applied Materials & Interfaces, 2020, 12(33): 37092-37099.
[64]	RONG Y S, MA Y H, GUO F Y, et al. Paintbrush-like Co doped Cu₃P grown on Cu foam as an efficient janus electrode for overall water splitting[J]. International Journal of Hydrogen Energy, 2019, 44(54): 28833-28840. doi: 10.1016/j.ijhydene.2019.09.042
[65]	WANG H L, WANG Y C, ZHANG J W, et al. Electronic structure engineering through Fe-doping CoP enables hydrogen evolution coupled with electro-Fenton[J]. Nano Energy, 2021, 84: 105943. doi: 10.1016/j.nanoen.2021.105943
[66]	XIAO X, TAO L M, LI M, et al. Electronic modulation of transition metal phosphide via doping as efficient and pH-universal electrocatalysts for hydrogen evolution reaction[J]. Chemical Science, 2018, 9(7): 1970-1975. doi: 10.1039/C7SC04849A
[67]	XU S R, YU X, LIU X, et al. Contrallable synthesis of peony-like porous Mn-CoP nanorod electrocatalyst for highly efficient hydrogen evolution in acid and alkaline[J]. Journal of Colloid and Interface Science, 2020, 577: 379-387. doi: 10.1016/j.jcis.2020.05.097
[68]	XUE H Y, MENG A, ZHANG H Q, et al. 3D urchin like V-doped CoP in situ grown on nickel foam as bifunctional electrocatalyst for efficient overall water-splitting[J]. Nano Research, 2021, 14: 4173-4181. doi: 10.1007/s12274-021-3359-2
[69]	YU X R, CHEN L X, JIA L Y, et al. Ion exchange synthesis of Fe-doped clustered CoP nanowires as superior electrocatalyst for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy, 2023, 48(44): 16715-16724. doi: 10.1016/j.ijhydene.2023.01.108
[70]	ZHANG Y, HUI Z X, ZHOU H Y, et al. Ga doping enables superior alkaline hydrogen evolution reaction performances of CoP[J]. Chemical Engineering Journal, 2022, 429: 132012. doi: 10.1016/j.cej.2021.132012
[71]	ZOU W J, XIANG J D, TANG H. Niobium-doped cobalt phosphide nanowires realizing enhanced electrocatalytic activity for overall water splitting[J]. International Journal of Hydrogen Energy, 2022, 47(27): 13251-13260.
[72]	XU W C, FAN G L, ZHU S L, et al. Electronic structure modulation of nanoporous cobalt phosphide by carbon doping for alkaline hydrogen evolution reaction[J]. Advanced Functional Materials, 2021, 31(48): 2107333.
[73]	BI H H, LI B, ZHAGN J, et al. Supersaturation-triggered synthesis of 2D/1D phosphide heterostructures as multi-functional catalysts for water splitting[J]. Applied Physics Letters, 2021, 118(9): 093901. doi: 10.1063/5.0041080
[74]	YE F, MA X F, CAO Y P, et al. Heterogeneous layered multiple transition metal composite electrocatalysts with controlled composition for hydrogen production[J]. International Journal of Hydrogen Energy, 2023, 48(5): 1733-1746. doi: 10.1016/j.ijhydene.2022.10.065
[75]	BOPPELLA R, TAN J W, YANG W, et al. Homologous CoP/NiCoP heterostructure on N-doped carbon for highly efficient and pH-universal hydrogen evolution electrocatalysis[J]. Advanced Functional Materials, 2019, 29(6): 1807976.
[76]	YANG Y X, ZHANG L, GUO F Y, et al. Curved trapezoidal Cu₃P/NiCoP nanosheet arrays on nickel-cobalt foam for pH-insensitive hydrogen evolution reaction[J]. Electrochimica Acta, 2022, 421: 140498. doi: 10.1016/j.electacta.2022.140498
[77]	JIAO Y Q, YAN H J, WANG D X, et al. Multi-touch cobalt phosphide-tungsten phosphide heterojunctions anchored on reduced graphene oxide boosting wide pH hydrogen evolution[J]. Science China Materials, 2022, 65: 1225-1236. doi: 10.1007/s40843-021-1894-4
[78]	RIYAJUDDIN S, TARIK AZIZ S K, KUMAR S, et al. 3D-graphene decorated with g-C₃N₄/Cu₃P composite: A noble metal-free bifunctional electrocatalyst for overall water splitting[J]. ChemCatChem, 2020, 12(5): 1394-1402.
[79]	WEI P, SUN X P, WANG M H, et al. Construction of an N-decorated carbon-encapsulated W₂C/WP heterostructure as an efficient electrocatalyst for hydrogen evolution in both alkaline and acidic media[J]. ACS Applied Materials & Interfaces, 2021, 13(45): 53955-53964.
[80]	HUI B, ZHANG K W, XIA Y Z, et al. Natural multi-channeled wood frameworks for electrocatalytic hydrogen evolution[J]. Electrochimica Acta, 2020, 330: 135274. doi: 10.1016/j.electacta.2019.135274
[81]	JIANG E J, JIANG J H, HUANG G, et al. Porous nanosheets of Cu₃P@N, P co-doped carbon hosted on copper foam as an efficient and ultrastable pH-universal hydrogen evolution electrocatalyst[J]. Sustainable Energy Fuels, 2021, 5(9): 2451-2457. doi: 10.1039/D1SE00161B
[82]	LI W X, CHEN Y F, YU B, et al. 3D hollow Co-Fe-P nanoframes immobilized on N, P-doped CNT as an efficient electrocatalyst for overall water splitting[J]. Nanoscale, 2019, 11(36): 17031-17040. doi: 10.1039/C9NR05924E
[83]	LIU S L, LIN Z S, WAN R D, et al. Cobalt phosphide supported by two-dimensional molybdenum carbide (MXene) for the hydrogen evolution reaction, oxygen evolution reaction, and overall water splitting[J]. Journal of Materials Chemistry A, 2021, 9(37): 21259-21269. doi: 10.1039/D1TA05648D
[84]	LU M J, LI L, CHEN D, et al. MOF-derived nitrogen-doped CoO@CoP arrays as bifunctional electrocatalysts for efficient overall water splitting[J]. Electrochimica Acta, 2020, 330: 135210. doi: 10.1016/j.electacta.2019.135210
[85]	SUMI V S, MEERA M S, SHA M A, et al. Effect of rGO on Fe₂O₃-TiO₂ composite incorporated NiP coating for boosting hydrogen evolution reaction in alkaline solution[J]. International Journal of Hydrogen Energy, 2020, 45(4): 2460-2477. doi: 10.1016/j.ijhydene.2019.11.167
[86]	WANG M Q, YE C, LIU H, et al. Nanosized metal phosphides embedded in nitrogen-doped porous carbon nanofibers for enhanced hydrogen evolution at all pH values[J]. Angewandte Chemie-International Edition, 2018, 57(7): 1963-1967.
[87]	WEI B, XU G C, HEI J C, et al. CoFeP hierarchical nanoarrays supported on nitrogen-doped carbon nanofiber as efficient electrocatalyst for water splitting[J]. Journal of Colloid and Interface Science, 2021, 602: 619-626. doi: 10.1016/j.jcis.2021.06.045
[88]	ZHANG X Y, WANG F L, FU J Y, et al. Amorphous-crystalline catalytic interface of CoFeOH/CoFeP with double sites based on ultrafast hydrolysis for hydrogen evolution at high current density[J]. Journal of Power Sources, 2021, 507: 230279. doi: 10.1016/j.jpowsour.2021.230279