An Efficient Mn-Ir Doped Supported Catalyst for PEM Water Electrolysis

doi:10.12096/j.2096-4528.pgt.22184

Abstract

Abstract:

Proton exchange membrane (PEM) water electrolysis is a green and sustainable method of hydrogen production. The development of efficient and economical electrocatalysts for anodic oxygen evolution reaction (OER) is the key to its large-scale commercialization. Iridium oxide catalysts supported by different manganese based oxide carriers (IrO _x /Mn₈O₁₀Cl₃, IrO _x /β-MnO₂ and IrO _x /α-MnO₂) were prepared by two-step synthesis method, and the content of iridium is about 55%. Compared with the commercial IrO₂ and other noble metal containing electrocatalysts, the synthesized catalysts have lower overpotential and higher current density. The overpotential of IrO _x /β-MnO₂ is only 228 mV at the current density of 10 mA/cm². The specific mass activity of IrO _x /Mn₈O₁₀Cl₃ reaches 916.7 A/g_Ir at 1.53V. The enhancement of OER activity is attributed to the abundant hydroxyl oxygen defects and Ir^III species on the catalyst surface. The rich crystalline-amorphous interface provides a large number of active sites for the reaction. The iridium oxide/manganese based oxide catalysts reported in this paper provide new insights for the development of efficient and economical catalysts for acidic OER.

Key words: proton exchange membrane water electrolysis, oxygen evolution reaction, manganese based oxide carriers, iridium oxide catalysts

CLC Number:

TK 91

Shuhan ZHANG, Xiaofeng MA, Ruilin ZHANG, Yanqun ZHU, Yong HE, Zhihua WANG. An Efficient Mn-Ir Doped Supported Catalyst for PEM Water Electrolysis[J]. Power Generation Technology, 2023, 44(3): 340-349.

Figures/Tables 8

References 40

1	DETZ R J， REEK J N H， VAN DER ZWAAN B C C ．The future of solar fuels：when could they become competitive[J]．Energy & Environmental Science，2018，11(7)：1653-1669． doi:10.1039/c8ee00111a
2	JACOBSON M Z， DELUCCHI M A ．Providing all global energy with wind，water，and solar power，part I： technologies，energy resources，quantities and areas of infrastructure，and materials[J]．Energy Policy，2011，39(3)：1154-1169． doi:10.1016/j.enpol.2010.11.040
3	李英峰，张涛，张衡，等．太阳能光伏光热高效综合利用技术[J]．发电技术，2022，43(3)：373-391． doi:10.12096/j.2096-4528.pgt.22052
	LI Y F， ZHANG T， ZHANG H，et al ．Efficient and comprehensive photovoltaic/photothermal utilization technologies for solar energy[J]．Power Generation Technology，2022，43(3)：373-391． doi:10.12096/j.2096-4528.pgt.22052
4	丁峰，李晓刚，梁泽琪，等．国外可再生能源发展经验及其对我国相关扶持政策的启示[J]．电力建设，2022，43(9)：1-11． doi:10.12204/j.issn.1000-7229.2022.09.001
	DING F， LI X G， LIANG Z Q，et al ．Review of foreign experience in promoting renewable energy development and inspiration to China[J]．Electric Power Construction，2022，43(9)：1-11． doi:10.12204/j.issn.1000-7229.2022.09.001
5	LIU Y， LIANG X， CHEN H，et al ．Iridium-containing water-oxidation catalysts in acidic electrolyte[J]．Chinese Journal of Catalysis，2021，42(7)：1054-1077． doi:10.1016/s1872-2067(20)63722-6
6	刘沅昆，张维静，张艳，等．面向新型电力系统的新能源与储能联合规划方法[J]．智慧电力，2022，50(10)：1-8． doi:10.3969/j.issn.1673-7598.2022.10.002
	LIU Y C， ZHANG W J， ZHANG Y，et al ．Joint planning method of renewable energy and energy storage for new-type power system[J]．Smart Power，2022，50(10)：1-8． doi:10.3969/j.issn.1673-7598.2022.10.002
7	孙伟卿，罗静，张婕．高比例风电接入的电力系统储能容量配置及影响因素分析[J]．电力系统保护与控制，2021，49(15)：9-18．
	ZHANG W Q， LUO J， ZHANG J ．Energy storage capacity allocation and influence factor analysis of a power system with a high proportion of wind power[J]．Power System Protection and Control，2021，49(15)：9-18．
8	陈晓光，杨秀媛，卜思齐，等．考虑经济功能性的风电场储能系统容量配置[J]．发电技术，2022，43(2)：341-352． doi:10.12096/j.2096-4528.pgt.21073
	CHEN X G， YANG X Y， BU S Q，et al ．Capacity allocation of wind farm energy storage system considering economic function[J]．Power Generation Technology，2022，43(2)：341-352． doi:10.12096/j.2096-4528.pgt.21073
9	CARMO M， FRITZ D L， MERGEL J，et al ．A comprehensive review on PEM water electrolysis[J]．International Journal of Hydrogen Energy，2013，38(12)：4901-4934． doi:10.1016/j.ijhydene.2013.01.151
10	REIER T， NONG H N， TESCHNER D，et al ．Electrocatalytic oxygen evolution reaction in acidic environments：reaction mechanisms and catalysts[J]．Advanced Energy Materials，2017，7(1)：1601275． doi:10.1002/aenm.201601275
11	田甜，李怡雪，黄磊，等．海上风电制氢技术经济性对比分析[J]．电力建设，2021，42(12)：136-144．
	TIAN T， LI Y X， HUANG L，et al ．Comparative analysis on the economy of hydrogen production technology for offshore wind power consumption[J]．Electric Power Construction，2021，42(12)：136-144．
12	顾玖，王晨磊，解大．电力市场环境下的电-氢一体化站优化运行[J]．电力科学与技术学报，2022，37(1)：130-139．
	GU J， WANG C L， XIE D ．Research on optimal operation of electricity-hydrogen integrated station in electricity market environment[J]．Journal of Electric Power Science and Technology，2022，37(1)：130-139．
13	张长云，黄景光，李振兴，等．极地环境含风氢储混合微电网容量优化配置[J]．电力工程技术，2022，41(1)：108-116． doi:10.12158/j.2096-3203.2022.01.015
	ZHANG C Y， HUANG J G， LI Z X，et al ．Optimal configuration of wind-hydrogen-storage hybrid microgrid capacity in polar environment[J]．Electric Power Engineering Technology，2022，41(1)：108-116． doi:10.12158/j.2096-3203.2022.01.015
14	KOPER M T M ．Thermodynamic theory of multi-electron transfer reactions： implications for electrocatalysis[J]．Journal of Electroanalytical Chemistry，2011，660(2)：254-260． doi:10.1016/j.jelechem.2010.10.004
15	BO X， DASTAFKAN K， ZHAO C ．Design of multi-metallic-based electrocatalysts for enhanced water oxidation[J]．ChemPhysChem，2019，20(22)：2936-2945． doi:10.1002/cphc.201900507
16	LEI Z， WANG T， ZHAO B，et al ．Recent progress in electrocatalysts for acidic water oxidation[J]．Advanced Energy Materials，2020，10(23)：2000478． doi:10.1002/aenm.202000478
17	SHAN J， ZHENG Y， SHI B，et al ．Regulating electrocatalysts via surface and interface engineering for acidic water electrooxidation[J]．ACS Energy Letters，2019，4(11)：2719-2730． doi:10.1021/acsenergylett.9b01758
18	JIN H，JOO J，N． CHAUDHARI K，et al ．Recent progress in bifunctional electrocatalysts for overall water splitting under acidic conditions[J]．ChemElectroChem，2019，6(13)：3244-3253． doi:10.1002/celc.201900507
19	MARSHALL A T， SUNDE S， TSYPKIN M，et al ．Performance of a PEM water electrolysis cell using Ir _x Ru _y Ta _z O₂ electrocatalysts for the oxygen evolution electrode[J]．International Journal of Hydrogen Energy，2007，32(13)：2320-2324． doi:10.1016/j.ijhydene.2007.02.013
20	OAKTON E， LEBEDEV D， POVIA M，et al ．IrO₂-TiO₂：a high-surface-area，active，and stable electrocatalyst for the oxygen evolution reaction[J]．ACS Catalysis，2017，7(4)：2346-2352． doi:10.1021/acscatal.6b03246
21	ABBOU S， CHATTOT R， MARTIN V，et al ．Manipulating the corrosion resistance of SnO₂ aerogels through doping for efficient and durable oxygen evolution reaction electrocatalysis in acidic media[J]．ACS Catalysis，2020，10(13)：7283-7294． doi:10.1021/acscatal.0c01084
22	GAO J， XU C Q， HUNG S F，et al ．Breaking long-range order in iridium oxide by alkali ion for efficient water oxidation[J]．Journal of the American Chemical Society，2019，141(7)：3014-3023． doi:10.1021/jacs.8b11456
23	JIANG B， KIM J， GUO Y，et al ．Efficient oxygen evolution on mesoporous IrO _x nanosheets[J]．Catalysis Science & Technology，2019，9(14)：3697-3702． doi:10.1039/c9cy00302a
24	ZHAO R， WANG Z， XU Q，et al ．Self-supported amorphous iridium oxide catalysts for highly efficient and durable oxygen evolution reaction in acidic media[J]．Electrochimica Acta，2021，391：138955． doi:10.1016/j.electacta.2021.138955
25	DU M， MENG Y， ZHU G，et al ．Intrinsic electrocatalytic activity of a single IrO _x nanoparticle towards oxygen evolution reaction[J]．Nanoscale，2020，12(43)：22014-22021． doi:10.1039/d0nr05780k
26	LI A， OOKA H， BONNET N，et al ．Stable potential windows for long-term electrocatalysis by manganese oxides under acidic conditions[J]．Angewandte Chemie International Edition，2019，58(15)：5054-5058． doi:10.1002/anie.201813361
27	FRYDENDAL R， PAOLI E A， CHORKENDORFF I，et al ．Toward an active and stable catalyst for oxygen evolution in acidic media：Ti-stabilized MnO₂ [J]．Advanced Energy Materials，2015，5(22)：1500991． doi:10.1002/aenm.201500991
28	KANG Q， VERNISSE L， REMSING R C，et al ．Effect of interlayer spacing on the activity of layered manganese oxide bilayer catalysts for the oxygen evolution reaction[J]．Journal of the American Chemical Society，2017，139(5)：1863-1870． doi:10.1021/jacs.6b09184
29	PAN S， LI H， LIU D，et al ．Efficient and stable noble-metal-free catalyst for acidic water oxidation[J]．Nature Communications，2022，13(1)：2294． doi:10.1038/s41467-022-30064-6
30	PASCUZZI M E C， HOFMANN J P， HENSEN E J M ．Promoting oxygen evolution of IrO₂ in acid electrolyte by Mn[J]．Electrochimica Acta，2021，366：137448． doi:10.1016/j.electacta.2020.137448
31	GHADGE S D， VELIKOKHATNYI O I， DATTA M K，et al ．Experimental and theoretical validation of high efficiency and robust electrocatalytic response of one-dimensional (1D) (Mn，Ir)O₂：10 F nanorods for the oxygen evolution reaction in PEM-based water electrolysis[J]．ACS Catalysis，2019，9(3)：2134-2157． doi:10.1021/acscatal.8b02901
32	SUN W， ZHOU Z， ZAMAN W Q，et al ．Rational manipulation of IrO₂ lattice strain on α-MnO₂ nanorods as a highly efficient water-splitting catalyst[J]．ACS Applied Materials & Interfaces，2017，9(48)：41855-41862． doi:10.1021/acsami.7b12775
33	HAN H， CHOI H， MHIN S，et al ．Advantageous crystalline-amorphous phase boundary for enhanced electrochemical water oxidation[J]．Energy & Environmental Science，2019，12(8)：2443-2454． doi:10.1039/c9ee00950g
34	LI G， LI S， GE J，et al ．Discontinuously covered IrO₂-RuO₂@Ru electrocatalysts for the oxygen evolution reaction： how high activity and long-term durability can be simultaneously realized in the synergistic and hybrid nano-structure[J]．Journal of Materials Chemistry A，2017，5(33)：17221-17229． doi:10.1039/c7ta05126c
35	HU W， ZHONG H， LIANG W，et al ．Ir-surface enriched porous Ir-Co oxide hierarchical architecture for high performance water oxidation in acidic media[J]．ACS Applied Materials & Interfaces，2014，6(15)：12729-12736． doi:10.1021/am5027192
36	DOSAEV K A， ISTOMIN S Y， ANTIPOV E V ．Synthesis and crystal structure of new oxochloride (Mn，Mg)₈Cl₃O₁₀ [J]．Russian Journal of Inorganic Chemistry，2022，67(7)：935-939． doi:10.1134/s0036023622070063
37	ZHANG Z， XIANG L， LIN F，et al ．Catalytic deep degradation of Cl-VOCs with the assistance of ozone at low temperature over MnO₂ catalysts[J]．Chemical Engineering Journal，2021，426：130814． doi:10.1016/j.cej.2021.130814
38	唐海荣．臭氧耦合催化氧化脱除烟气中NO _x 和Cl-VOCs的试验与机理研究[D]．杭州：浙江大学，2022．
	TANG H R ．Experimental and mechanism investigation on catalytic ozonation for removal of NO _x and Cl-VOCs in flue gas[D]．Hangzhou：Zhejiang University，2022．
39	LIANG X， HART C， PANG Q，et al ．A highly efficient polysulfide mediator for lithium-sulfur batteries[J]．Nature Communications，2015，6(1)：5682． doi:10.1038/ncomms6682
40	MINGUZZI A， LOCATELLI C， LUGARESI O，et al ．Easy accommodation of different oxidation states in iridium oxide nanoparticles with different hydration degree as water oxidation electrocatalysts[J]．ACS Catalysis，2015，5(9)：5104-5115． doi:10.1021/acscatal.5b01281

催化剂	电解液	10 mA/cm²时过电位/mV	Tafel斜率/(mV/dec)	参考文献
IrO₂@α-MnO₂	0.1 mol/L HClO₄	275	59	[32]
(Mn_0.8Ir_0.2)O₂	0.5 mol/L H₂SO₄	240	46	[31]
(Ir_0.3Mn_0.7)O₂	0.1 mol/L H₂SO₄	383	49	[30]
IrO₂-RuO₂@Ru	0.5 mol/L H₂SO₄	281	53.1	[34]
Ir_0.7Co_0.3O _x	0.5 mol/L H₂SO₄	320	40	[35]
IrO₂/Ti	0.1 mol/L HClO₄	250	50.4	[24]
Li-IrO _x	0.5 mol/L H₂SO₄	300	39	[22]
Mn_7.5O₁₀Br₃	0.5 mol/L H₂SO₄	295	68	[29]
IrO _x /α-MnO₂	0.5 mol/L H₂SO₄	245	64	本文
IrO _x /β-MnO₂	0.5 mol/L H₂SO₄	228	46	本文
IrO _x /Mn₈O₁₀Cl₃	0.5 mol/L H₂SO₄	230	45	本文

催化剂	电解液	10 mA/cm²时过电位/mV	Tafel斜率/(mV/dec)	参考文献
IrO₂@α-MnO₂	0.1 mol/L HClO₄	275	59	[32]
(Mn_0.8Ir_0.2)O₂	0.5 mol/L H₂SO₄	240	46	[31]
(Ir_0.3Mn_0.7)O₂	0.1 mol/L H₂SO₄	383	49	[30]
IrO₂-RuO₂@Ru	0.5 mol/L H₂SO₄	281	53.1	[34]
Ir_0.7Co_0.3O _x	0.5 mol/L H₂SO₄	320	40	[35]
IrO₂/Ti	0.1 mol/L HClO₄	250	50.4	[24]
Li-IrO _x	0.5 mol/L H₂SO₄	300	39	[22]
Mn_7.5O₁₀Br₃	0.5 mol/L H₂SO₄	295	68	[29]
IrO _x /α-MnO₂	0.5 mol/L H₂SO₄	245	64	本文
IrO _x /β-MnO₂	0.5 mol/L H₂SO₄	228	46	本文
IrO _x /Mn₈O₁₀Cl₃	0.5 mol/L H₂SO₄	230	45	本文

催化剂	Ir原子分数/%	Mn原子分数/%	Cl原子分数/%	O原子分数/%	Ir质量分数/%
IrO _x /Mn₈O₁₀Cl₃	14.40	21.40	7.49	56.71	54.10
IrO _x /β-MnO₂	14.19	20.98	—	64.83	55.47
IrO _x /α-MnO₂	12.45	21.00	—	66.55	51.89

催化剂	Ir原子分数/%	Mn原子分数/%	Cl原子分数/%	O原子分数/%	Ir质量分数/%
IrO _x /Mn₈O₁₀Cl₃	14.40	21.40	7.49	56.71	54.10
IrO _x /β-MnO₂	14.19	20.98	—	64.83	55.47
IrO _x /α-MnO₂	12.45	21.00	—	66.55	51.89

催化剂	O_metal-O		O_OH		O_H2O		Ir^III相对面积/%
催化剂	结合能/eV	相对面积/%	结合能/eV	相对面积/%	结合能/eV	相对面积/%	Ir^III相对面积/%
IrO _x /Mn₈O₁₀Cl₃	530.00	27.97	531.42	46.46	532.62	25.57	28.92
IrO _x /β-MnO₂	530.20	29.62	531.50	45.52	532.60	24.86	27.89
IrO _x /α-MnO₂	529.92	33.39	531.45	42.60	532.62	24.01	26.44