面向电解水的激光制备微纳米结构催化电极

蔡明勇; 江国琛; 钟敏霖

doi:doi:10.3788/CJL202148.0202008

中国激光, 2021, 48 (2): 0202008, 网络出版: 2021-01-06

面向电解水的激光制备微纳米结构催化电极下载： 1544次特邀综述

Laser Fabricated Electrodes with Micro-Nano Structures for Electrocatalytic Water Splitting

蔡明勇江国琛钟敏霖 ^*

作者单位

清华大学材料学院激光材料加工研究中心, 北京 100084

图 & 表

图 1. 电解水示意图^[5]

Fig. 1. Schematic illustration of electrolysis of water^[5]

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图 2. 催化活性的评估。(a)极化曲线示意图;(b)Tafel斜率示意图

Fig. 2. Evaluation of catalytic activity. (a) Schematic illustration of polarization curve; (b) schematic illustration of Tafel slope

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图 3. 激光与溶液作用的几个典型实例。(a)过渡金属氢氧化物的合成示意图^[22];(b)(c)过渡金属氢氧化物的SEM图片^[22];(d)过渡金属氢氧化物初始状态与2h后过电压的比较^[22];(e)无定型MoS_x的合成示意图、分子结构以及析氢催化机理^[65];(f)无定型MoS_x的TEM图片(插图为相应的SAED花样)^[65]

Fig. 3. Several typical examples of the interaction between laser and solution. (a) Schematic illustration of the preparation process of transition metal hydroxides^[22]; (b)(c) SEM images of transition metal hydroxides^[22]; (d) overpotential values of transition metal hydroxides at time =0 and time =2h^[22]; (e) schematic illustration of the preparation pro

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图 4. 激光与颗粒作用的几个典型实例。(a)激光破碎Co₃O₄的合成示意图^[24];(b)激光破碎Co₃O₄的DFT计算模型^[24];(c)激光破碎Co₃O₄的析氧极化曲线^[24];(d)激光辐照MoS₂的合成示意图^[66];(e)激光辐照MoS₂的析氢极化曲线^[66];(f)激光液相辐照制备氮掺杂GO的实验装置示意图^[

Fig. 4. Several typical examples of the interaction between laser and particles. (a) Schematic illustration of the synthesis of laser-fragmentated Co₃O₄; (b) structural modes for DFT calculation of laser-fragmentated Co₃O₄; (c) OER polarization curves of laser-fragmentated Co₃ $O_{4}$
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图 5. 激光与块体靶材作用的几个典型实例。(a) NiFe LDH的析氧反应过程示意图^[86];(b) NiO/NiFe LDH的透射电镜(TEM)图片^[40];(c) NiO/NiFe LDH的析氧极化曲线^[40];(d) NiO/NiFe LDH的DFT计算模型^[40];(e) RuAu单原子合金的合成示意图^[71];(f)(g) RuAu单原子合金的HAADF-STEM图片^[71];(h) RuAu

Fig. 5. Several typical examples of the interaction between laser and bulk targets. (a) Schematic illustration of the OER process of NiFe LDH^[86]; (b) TEM image of NiO/NiFe LDH^[40]; (c) OER polarization curves of NiO/NiFe LDH^[40]; (d) structural models for DFT calculation of NiO/NiFe LDH^[40]; (e) schematic

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图 6. 结构和电化学特征示意图^[14]。(a)传统的粉末催化剂;(b)自支撑微纳米结构催化电极

Fig. 6. Schematic illustration of the structural and electrochemical features^[14]. (a) Conventional powdery catalysts; (b) self-supported micro-nano electrode

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图 7. 脉冲激光制备的自支撑微纳米结构。(a)分散纳米颗粒^[90];(b)纳米波纹^[91];(c)绒毛状团簇^[45];(d)菜花状团聚体^[94];(e)分层级微纳米结构^[95];(f)纳米线^[98];(g)纳米片^[98];(h)纳米草^{[Fig. 7. Self-supported micro-nano structures fabricated by pulse laser. (a) Dispersive nanoparticles^[90]; (b) nanoripples^[91]; (c) fluff-like clusters^[45]; (d) cauliflower-like aggregates^[94]; (e) hierarchical micro-nano structures^[95]; (f) nanowires^{[
下载图片查看原文}}

图 8. 激光直接制备自支撑微纳米结构催化电极的几个典型实例。(a)激光烧蚀镍片的全解水极化曲线^[45];(b)激光烧蚀镍片的稳定性测试结果^[45];(c)全解水装置照片^[45];(d)三维分布的Fe₃O₄纳米颗粒团簇的SEM图片^[47];(e)三维分布的Fe₃O₄纳米颗粒团簇的稳定性测试结果^[47];(f)NiS₂/MoS₂异质结的合成示意图^{[Fig. 8. Several typical examples of self-supported catalytic electrodes with micro-nano structures directly fabricated by laser. (a) Polarization curves for overall water splitting of laser-ablated Ni plates^[45]; (b) stability test of laser-ablated Ni plates^[45]; (c) digital photograph of the overall water splitting device^[45]; (d) SEM image of three-dimen
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图 9. 激光复合其他化学法制备自支撑微纳米结构催化电极的几个典型实例。(a)(b)CoS₂/WS₂纳米复合物的SEM图片和TEM图片^[77];(c)(d)NiO/CoFe LDH分层级纳米结构的合成示意图和全解水极化曲线^[50]

Fig. 9. Several typical examples of self-supported catalytic electrodes with micro-nano structures fabricated by laser hybrid with other chemical methods. (a)(b) SEM image and TEM image of CoS₂/WS₂hybrid catalysts^[77]; (c)(d) schematic illustration of the preparation process of NiO/CoFe LDH hierarchical nanostructures and polarization curves for overall water splitting^[50]

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图 10. 大面积制备的可行性验证。(a)(b)低碳钢催化电极的大面积样品照片和稳定性测试结果^[46];(c)~(f)不锈钢丝网电极的大面积样品照片、SEM图片和两电极极化曲线^[47]

Fig. 10. Feasibility verification of large-area preparation. (a)(b) Digital photograph of large-area sample and stability test of the mild steel electrode^[46]; (c)--(f) digital photograph and SEM images of large-area sample, and two-electrode polarization curves^[47]

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表 1基于激光微纳制造技术制备的电解水催化剂的性能总结

Table1. Summary of the catalytic activity of various catalysts based on laser micro-nano fabrication

Catalyst	Type	Electrolyte	Overpotential (at currentdensity of 10 mA·cm^-2)/mV	Tafel slope/(mV·dec^-1)	Ref.
Amorphous Ni-Co-OH	OER	1mol·L^-1 NaOH	337	74.65	[22]
Laser-ablated CoNiPO₄	OER	1mol·L^-1 KOH	238	46	[23]
Laser-fragmentated Co₃O₄	OER	1mol·L^-1 KOH	294	74	[24]
Laser-fragmentated FeCo₂O₄	OER	1mol·L^-1 KOH	276	61.6	[25]
Laser-fragmentated CoFe₂O₄	OER	1mol·L^-1 KOH	320	71	[26]
Catalyst	Type	Electrolyte	Overpotential (at current density of 10 mA·cm^-2) /mV	Tafel slope/ (mV·dec^-1)	Ref.
Laser-fragmentated CoO	OER	1mol·L^-1 KOH	369	46	[27]
Laser-irradiated IrO₂@Ir	OER	1mol·L^-1 KOH	255	45	[28]
NiCo₂O₄/NLG	OER	1mol·L^-1 KOH	310	87.5	[29]
CoO/NLG	OER	1mol·L^-1 KOH	295	76.4	[30]
N-doped CNT	OER	0.1mol·L^-1 KOH	360	59	[31]
Co₃O_4-_x/NG	OER	1mol·L^-1 KOH	357	86.7	[32]
Ti/La-doped NiFe LDH	OER	1mol·L^-1 KOH	260	44.7	[33]
PtCo/CoO_x	OER	1mol·L^-1 KOH	380	71.2	[34]
FeO_x NPs	OER	0.2mol·L^-1 phosphate buffer	—	110	[35]
CoO NPs	OER	0.4mol·L^-1 NaSO₄	—	128	[36]
Au_0.89Fe_0.11 nanoalloy	OER	1mol·L^-1 KOH	800	163	[37]
Co_0.75Ni_0.25(OH)₂ NSs	OER	1mol·L^-1 KOH	235	56	[38]
CoO/CoFe LDH	OER	1mol·L^-1 KOH	254	34	[39]
NiO/NiFe LDH	OER	1mol·L^-1 KOH	180	30	[40]
Co₃O₄ NPs	OER	1mol·L^-1 KOH	271	42	[41]
O_v-modified CoOOH	OER	1mol·L^-1 KOH	330	63.2	[42]
Ir nanospheres	OER	0.5mol·L^-1 H₂SO₄	266	58.7	[43]
Laser-irradiated CoFe₂O₄	OER	1mol·L^-1 NaOH	460	—	[44]
NiO NPs	OER	1mol·L^-1 KOH	294	41	[45]
Ni-doped Fe₃O₄ NPs	OER	1mol·L^-1 KOH	272	39.4	[46]
3D Fe₃O₄ NPs	OER	1mol·L^-1 KOH	262	35.0	[47]
Defect-rich NiFe-oxides	OER	1mol·L^-1 KOH	223	35.0	[48]
Micro/nano Cu-oxides	OER	1mol·L^-1 KOH	—	63	[49]
Ni/NiO@CoFe LDH	OER	1mol·L^-1 KOH	230	34.3	[50]
Cu/Cu-oxides/Co(OH)₂	OER	1mol·L^-1 KOH	—	58	[51]
Laser-rusted stainless steel	OER	1mol·L^-1 KOH	382	52	[52]
Laser-processed Ni₆Fe₄	OER	1mol·L^-1 KOH	464(at current density of 100 mA·cm^-2)	46	[53]
Laser-structured NiFe electrode	OER	32.5% KOH(mass fraction)	249	39	[54]
Nanoporous NiFe alloy	OER	1mol·L^-1 KOH	442	36	[55]
LIG-NiFe	OER	1mol·L^-1 KOH	296	50	[56]
Co₃O₄/LIG	OER	0.1mol·L^-1 KOH	340	40	[57]
NiFe/LIG	OER	1mol·L^-1 KOH	240	32.8	[58]
LIG-NiFe LIG-Co-P	OER	1mol·L^-1 KOH	292 364	49 84	[59]
Oxidized LIG	OER	1mol·L^-1 KOH	260	49	[60]
LIG-CoNiFe	OER	0.1mol·L^-1 KOH	287	41	[61]
Laser-induced MoS₂/C	HER	0.5mol·L^-1 H₂SO₄	216	64	[62]
MoS₂ QDs	HER	0.5mol·L^-1 H₂SO₄	108	53	[63]
Laser-reduced Pt-MoS₂	HER	0.5mol·L^-1 H₂SO₄	41	25	[64]
Amorphous MoS_x	HER	0.5mol·L^-1 H₂SO₄	145	40	[65]
Catalyst	Type	Electrolyte	Overpotential (at current density of 10 mA·cm^-2) /mV	Tafel slope/ (mV·dec^-1)	Ref.
Laser-ablated MoS₂	HER	0.5mol·L^-1 H₂SO₄	178	41.4	[66]
Laser-exfoliated MoS₂	HER	0.5mol·L^-1 H₂SO₄	180	54	[67]
NiS nanostructures	HER	1mol·L^-1 KOH	—	218	[68]
SnS₂NPs	HER	1mol·L^-1 H₂SO₄	—	115.8	[69]
Laser-induced NGO	HER	0.5mol·L^-1 H₂SO₄	>550	133.81	[70]
Co_0.75Ni_0.25(OH)₂ NSs	HER	1mol·L^-1 KOH	95	85	[38]
RuAu single-atom alloy	HER	1mol·L^-1 KOH	24	37	[71]
Ag NPs	HER	0.5mol·L^-1 H₂SO₄	96	76.1	[72]
Fault-stacked Ag NPs	HER	0.5mol·L^-1 H₂SO₄	32	31	[73]
Ir nanospheres	HER	0.5mol·L^-1 H₂SO₄	28	17.8	[43]
Rh NPs	HER	0.1mol·L^-1 H₂SO₄	57	55	[74]
NiO NPs	HER	1mol·L^-1 KOH	121	88	[45]
Laser-structured Ni	HER	29.9% KOH(mass fraction)	280(at current density of 300 mA·cm^-2)	89	[75]
Laser-structured Ti/Pt	HER	1mol·L^-1 KOH	158(at current density of 300 mA·cm^-2)	141	[76]
CoS₂/WS₂hybrids	HER	0.5mol·L^-1 H₂SO₄	119	68	[77]
NiS₂/MoS₂ heterostructures	HER	1mol·L^-1 KOH 1mol·L^-1 phosphate buffer	98 157	88 109	[78]
Ni/NiO@CoFe LDH	HER	1mol·L^-1 KOH	107	56.9	[50]
MoS₂-LIG	HER	0.5mol·L^-1 H₂SO₄	—	97	[79]
Pt/LSG	HER	0.5mol·L^-1 H₂SO₄	131	72	[80]
LIG-Pt LIG-Co-P	HER	1mol·L^-1 KOH	107 141	83 54	[59]

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蔡明勇, 江国琛, 钟敏霖. 面向电解水的激光制备微纳米结构催化电极[J]. 中国激光, 2021, 48(2): 0202008. Cai Mingyong, Jiang Guochen, Zhong Minlin. Laser Fabricated Electrodes with Micro-Nano Structures for Electrocatalytic Water Splitting[J]. Chinese Journal of Lasers, 2021, 48(2): 0202008.

面向电解水的激光制备微纳米结构催化电极下载： 1544次特邀综述

图 1. 电解水示意图^[5]

Fig. 1. Schematic illustration of electrolysis of water^[5]

图 2. 催化活性的评估。(a)极化曲线示意图;(b)Tafel斜率示意图

Fig. 2. Evaluation of catalytic activity. (a) Schematic illustration of polarization curve; (b) schematic illustration of Tafel slope

图 6. 结构和电化学特征示意图^[14]。(a)传统的粉末催化剂;(b)自支撑微纳米结构催化电极

Fig. 6. Schematic illustration of the structural and electrochemical features^[14]. (a) Conventional powdery catalysts; (b) self-supported micro-nano electrode

Fig. 7. Self-supported micro-nano structures fabricated by pulse laser. (a) Dispersive nanoparticles^[90]; (b) nanoripples^[91]; (c) fluff-like clusters^[45]; (d) cauliflower-like aggregates^[94]; (e) hierarchical micro-nano structures^[95]; (f) nanowires^{[
下载图片查看原文}

图 9. 激光复合其他化学法制备自支撑微纳米结构催化电极的几个典型实例。(a)(b)CoS₂/WS₂纳米复合物的SEM图片和TEM图片^[77];(c)(d)NiO/CoFe LDH分层级纳米结构的合成示意图和全解水极化曲线^[50]

图 10. 大面积制备的可行性验证。(a)(b)低碳钢催化电极的大面积样品照片和稳定性测试结果^[46];(c)~(f)不锈钢丝网电极的大面积样品照片、SEM图片和两电极极化曲线^[47]

Fig. 10. Feasibility verification of large-area preparation. (a)(b) Digital photograph of large-area sample and stability test of the mild steel electrode^[46]; (c)--(f) digital photograph and SEM images of large-area sample, and two-electrode polarization curves^[47]

表 1基于激光微纳制造技术制备的电解水催化剂的性能总结

Table1. Summary of the catalytic activity of various catalysts based on laser micro-nano fabrication

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面向电解水的激光制备微纳米结构催化电极 下载： 1544次特邀综述

图 1. 电解水示意图[5]

Fig. 1. Schematic illustration of electrolysis of water[5]

图 2. 催化活性的评估。(a)极化曲线示意图;(b)Tafel斜率示意图

Fig. 2. Evaluation of catalytic activity. (a) Schematic illustration of polarization curve; (b) schematic illustration of Tafel slope

图 6. 结构和电化学特征示意图[14]。(a)传统的粉末催化剂;(b)自支撑微纳米结构催化电极

Fig. 6. Schematic illustration of the structural and electrochemical features[14]. (a) Conventional powdery catalysts; (b) self-supported micro-nano electrode

Fig. 7. Self-supported micro-nano structures fabricated by pulse laser. (a) Dispersive nanoparticles[90]; (b) nanoripples[91]; (c) fluff-like clusters[45]; (d) cauliflower-like aggregates[94]; (e) hierarchical micro-nano structures[95]; (f) nanowires[ 下载图片 查看原文

图 9. 激光复合其他化学法制备自支撑微纳米结构催化电极的几个典型实例。(a)(b)CoS2/WS2纳米复合物的SEM图片和TEM图片[77];(c)(d)NiO/CoFe LDH分层级纳米结构的合成示意图和全解水极化曲线[50]

图 10. 大面积制备的可行性验证。(a)(b)低碳钢催化电极的大面积样品照片和稳定性测试结果[46];(c)~(f)不锈钢丝网电极的大面积样品照片、SEM图片和两电极极化曲线[47]

Fig. 10. Feasibility verification of large-area preparation. (a)(b) Digital photograph of large-area sample and stability test of the mild steel electrode[46]; (c)--(f) digital photograph and SEM images of large-area sample, and two-electrode polarization curves[47]

表 1基于激光微纳制造技术制备的电解水催化剂的性能总结

Table1. Summary of the catalytic activity of various catalysts based on laser micro-nano fabrication

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面向电解水的激光制备微纳米结构催化电极下载： 1544次特邀综述

图 1. 电解水示意图^[5]

Fig. 1. Schematic illustration of electrolysis of water^[5]

图 6. 结构和电化学特征示意图^[14]。(a)传统的粉末催化剂;(b)自支撑微纳米结构催化电极

Fig. 6. Schematic illustration of the structural and electrochemical features^[14]. (a) Conventional powdery catalysts; (b) self-supported micro-nano electrode

Fig. 7. Self-supported micro-nano structures fabricated by pulse laser. (a) Dispersive nanoparticles^[90]; (b) nanoripples^[91]; (c) fluff-like clusters^[45]; (d) cauliflower-like aggregates^[94]; (e) hierarchical micro-nano structures^[95]; (f) nanowires^{[
下载图片查看原文}

图 9. 激光复合其他化学法制备自支撑微纳米结构催化电极的几个典型实例。(a)(b)CoS₂/WS₂纳米复合物的SEM图片和TEM图片^[77];(c)(d)NiO/CoFe LDH分层级纳米结构的合成示意图和全解水极化曲线^[50]

图 10. 大面积制备的可行性验证。(a)(b)低碳钢催化电极的大面积样品照片和稳定性测试结果^[46];(c)~(f)不锈钢丝网电极的大面积样品照片、SEM图片和两电极极化曲线^[47]

Fig. 10. Feasibility verification of large-area preparation. (a)(b) Digital photograph of large-area sample and stability test of the mild steel electrode^[46]; (c)--(f) digital photograph and SEM images of large-area sample, and two-electrode polarization curves^[47]