过渡金属磷化物的改性方法及其在电化学析氢中的应用

doi:10.16085/j.issn.1000-6613.2022-1682

摘要/Abstract

摘要：

过渡金属磷化物催化活性高、稳定性好，是电催化析氢的良好催化剂。然而，实现过渡金属磷化物在电解水制氢领域的大规模应用，还需要进一步提升其催化性能。本文以过渡金属磷化物的组成变化为出发点，从金属/磷（M/P）化学计量比的角度对过渡金属磷化物的性能进行了总结，介绍了其常见的制备方法，详细综述了元素掺杂、构造缺陷、构建界面工程、耦合炭材料、调控微观结构、改善材料浸润性等改性方法对过渡金属磷化物电催化制氢性能的影响。最后在新型磷源的开发、测试标准化、晶面调控等方面对过渡金属磷化物的发展趋势进行了展望。

关键词: 过渡金属磷化物, 催化剂, 电解, 制氢

Abstract:

Transition metal phosphides are efficient catalytic materials for electrochemical hydrogen production because of their high catalytic activity and good stability. However, realizing their large-scale application in electrolytic water hydrogen evolution needs further improvement on the catalytic performance. Based on the composition of transition metal phosphides, their properties were summarized in terms of the metal/phosphorus (M/P) stoichiometric ratio. In addition, the common preparation methods of transition metal phosphides were introduced, and the influence of the modification methods such as element doping, structural defects, interface engineering and coupling of carbon materials, microstructure regulation, and wettability improvement on the electrocatalytic hydrogen evolution were reviewed in detail as well. The development trend of transition metal phosphides is also prospected from the aspects of exploiting new phosphorus source, standardizing electrochemical tests and regulating the crystal planes.

Key words: transition metal phosphides, catalyst, electrolysis, hydrogen production

中图分类号:

TQ116.21

王蕴青, 杨国锐, 延卫. 过渡金属磷化物的改性方法及其在电化学析氢中的应用[J]. 化工进展, 2023, 42(7): 3532-3549.

WANG Yunqing, YANG Guorui, YAN Wei. Transition metal phosphide modification and its applications in electrochemical hydrogen evolution reaction[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3532-3549.

图/表 16

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催化剂	电解质	过电位η₁₀/mV	Tafel斜率/mV·dec^-1	电化学稳定性	参考文献
NiP₂ NS/CC	0.5mol/L H₂SO₄	75	51	3000CV	[24]
NiP/RGO	0.5mol/L H₂SO₄	89（η_起始）	135.1	500CV	[25]
	1mol/L KOH	116（η_起始）	122.4
NiP _x /TNAs	1mol/L KOH	104	70.1	—	[26]
NiP@C	1mol/L KOH	23（η₁₀₀）	12.4	10/20mA/cm²（10h）	[27]
NiP/NF	1mol/L KOH	102	90	1000CV	[28]
Ni₂P/Ni/NF	1mol/L KOH	94	72	10mA/cm²（20h）	[29]
V-Ni₂P/NF	1mol/L KOH	55	48	10mA/cm²（50h）	[30]
Ni-Ni₃P@NPC	0.5mol/L H₂SO₄	73	57.93	30/60mA/cm²（25h）	[31]
Ni₃P PHNs	0.5mol/L H₂SO₄	85	50	2000CV	[32]
	1mol/L KOH	338（η₂₀）	190
N-Ni₅P₄	1mol/L KOH	96	62.2	1000CV	[33]
Ni₅P₄/NF	1mol/L KOH	64	64	3000CV	[34]
Cuf@Ni₅P₄	0.5mol/L H₂SO₄	90	49	10/160mA/cm²（84h）	[35]
Ni₁₂P₅/CNT	0.5mol/L H₂SO₄	129	56	1000CV	[36]
Ni₁₂P₅ NCs	0.5mol/L H₂SO₄	118	42	500CV	[37]

催化剂	电解质	过电位η₁₀/mV	Tafel斜率/mV·dec^-1	电化学稳定性	参考文献
NiP₂ NS/CC	0.5mol/L H₂SO₄	75	51	3000CV	[24]
NiP/RGO	0.5mol/L H₂SO₄	89（η_起始）	135.1	500CV	[25]
	1mol/L KOH	116（η_起始）	122.4
NiP _x /TNAs	1mol/L KOH	104	70.1	—	[26]
NiP@C	1mol/L KOH	23（η₁₀₀）	12.4	10/20mA/cm²（10h）	[27]
NiP/NF	1mol/L KOH	102	90	1000CV	[28]
Ni₂P/Ni/NF	1mol/L KOH	94	72	10mA/cm²（20h）	[29]
V-Ni₂P/NF	1mol/L KOH	55	48	10mA/cm²（50h）	[30]
Ni-Ni₃P@NPC	0.5mol/L H₂SO₄	73	57.93	30/60mA/cm²（25h）	[31]
Ni₃P PHNs	0.5mol/L H₂SO₄	85	50	2000CV	[32]
	1mol/L KOH	338（η₂₀）	190
N-Ni₅P₄	1mol/L KOH	96	62.2	1000CV	[33]
Ni₅P₄/NF	1mol/L KOH	64	64	3000CV	[34]
Cuf@Ni₅P₄	0.5mol/L H₂SO₄	90	49	10/160mA/cm²（84h）	[35]
Ni₁₂P₅/CNT	0.5mol/L H₂SO₄	129	56	1000CV	[36]
Ni₁₂P₅ NCs	0.5mol/L H₂SO₄	118	42	500CV	[37]

催化剂	电解质	过电位η₁₀/mV	Tafel斜率/mV·dec^-1	电化学稳定性	参考文献
CoP/GF	1mol/L KOH	130（η₂₀）	80.1	50h	[39]
CoP	0.5mol/L H₂SO₄	84	61	1000CV	[40]
	1mol/L KOH	94	67
CoP/Co₂P	0.5mol/L H₂SO₄	87	58	10mA/cm²（24h）	[41]
	1mol/L KOH	133	60
CoP-NC	0.5mol/L H₂SO₄	145	55	2000CV	[42]
	1mol/L KOH	167	57
	1mol/L PBS	252	110
CoP/CN/Ni	0.5mol/L H₂SO₄	66	39.5	10mA/cm²（12h）	[43]
	1mol/L KOH	106	53.4
CoP	1mol/L KOH	71	60.75	3000CV	[44]
CoP/Co₂P	0.5mol/L H₂SO₄	81	36.2	2000CV	[45]
	1mol/L KOH	109	78.9
	1mol/L PBS	227	190.1
Co₂P NF	0.5mol/L H₂SO₄	178	32	1000CV	[46]
	1mol/L KOH	190	61

催化剂	电解质	过电位η₁₀/mV	Tafel斜率/mV·dec^-1	电化学稳定性	参考文献
CoP/GF	1mol/L KOH	130（η₂₀）	80.1	50h	[39]
CoP	0.5mol/L H₂SO₄	84	61	1000CV	[40]
	1mol/L KOH	94	67
CoP/Co₂P	0.5mol/L H₂SO₄	87	58	10mA/cm²（24h）	[41]
	1mol/L KOH	133	60
CoP-NC	0.5mol/L H₂SO₄	145	55	2000CV	[42]
	1mol/L KOH	167	57
	1mol/L PBS	252	110
CoP/CN/Ni	0.5mol/L H₂SO₄	66	39.5	10mA/cm²（12h）	[43]
	1mol/L KOH	106	53.4
CoP	1mol/L KOH	71	60.75	3000CV	[44]
CoP/Co₂P	0.5mol/L H₂SO₄	81	36.2	2000CV	[45]
	1mol/L KOH	109	78.9
	1mol/L PBS	227	190.1
Co₂P NF	0.5mol/L H₂SO₄	178	32	1000CV	[46]
	1mol/L KOH	190	61

催化剂	电解质	过电位η₁₀/mV	Tafel斜率/mV·dec^-1	电化学稳定性	参考文献
FeP@PPy/CTs	0.5mol/L H₂SO₄	103.1	49.2	46h	[49]
FeP HNPs	0.5mol/L H₂SO₄	76	55	10mA/cm²（5h）	[50]
FeP	0.5mol/L H₂SO₄	154	65	160mV（6000s）	[51]
Vc-FeP	0.5mol/L H₂SO₄	65	49	10mA/cm²（7d）	[52]
	1mol/L KOH	108	62
CFP-FeP HNA	0.5mol/L H₂SO₄	45（η₂₀）	53	12h	[53]
	1mol/L KOH	221（η₂₀）	134
FeP NPs	0.5mol/L H₂SO₄	76	60	10mA/cm²（12h）	[54]
Fe₂P/GCS	0.5mol/L H₂SO₄	88	49	2000CV	[55]
Fe₂P-ND/FG	0.5mol/L H₂SO₄	91	47	4000CV	[56]
	1mol/L KOH	168	74
	1mol/L PBS	349	113
Fe₃P	0.5mol/L H₂SO₄	49	57	120mV（20h）	[21]
Fe₃P	0.5mol/L H₂SO₄	160	149	5h	[57]