A review on fundamentals for designing stable ruthenium-based catalysts for the hydrogen and oxygen evolution reactions

doi:10.1016/S1872-2067(24)60013-6

Chinese Journal of Catalysis ›› 2024, Vol. 60: 68-106.DOI: 10.1016/S1872-2067(24)60013-6

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A review on fundamentals for designing stable ruthenium-based catalysts for the hydrogen and oxygen evolution reactions

Wangyan Gou^a^,^b, Yichen Wang^a^,^b, Mingkai Zhang^c, Xiaohe Tan^a, Yuanyuan Ma^a^,^b^,^*(), Yongquan Qu^b^,^*()

^aResearch & Development Institute of Northwestern Polytechnical University in Shenzhen, Shenzhen 518057, Guangdong, China
^bSchool of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710072, Shaanxi, China
^cSchool of Science, Xi’an University of Technology, Xi’an 710048, Shaanxi, China

Received:2023-12-08 Accepted:2024-03-15 Online:2024-05-18 Published:2024-05-20
Contact: *E-mail: yyma@nwpu.edu.cn (Y. Ma), yongquan@nwpu.edu.cn (Y. Qu).
About author:Yuanyuan Ma (School of Chemistry and Chemical Engineering, Northwestern Polytechnical University) is a professor at the School of Chemistry and Chemical Engineering, Northwestern Polytechnical University. She received her B.S. in Materials Science and Engineering from Nanjing University in 2001 and Ph.D from the University of California, Davis in 2012. Her current research focuses on the design of highly performed electrocatalysts for water splitting and organic transformations as well as the reaction mechanisms for electrochemical reactions.
Yongquan Qu (School of Chemistry and Chemical Engineering, Northwestern Polytechnical University) is a professor at the School of Chemistry and Chemical Engineering, Northwestern Polytechnical University. He received his B.S. in Materials Science and Engineering from Nanjing University in 2001, M.S. in Chemistry from the Dalian Institute of Chemical Physics in 2004, and Ph.D in Chemistry from the University of California, Davis, in 2009. He worked as a postdoctoral research fellow in the University of California, Los Angeles, from 2009 to 2011. His research interests focus on heterogeneous catalysis in the areas of organic synthesis, clean energy production and biomimetic catalysis.
Supported by:
Basic and Applied Basic Research Foundation of Guangdong Province(2023A1515012288);Natural Science Foundation of Shaanxi province, China(2022JQ-433);China Postdoctoral Science Foundation(2022M722585);Fundamental Research Funds for the Central Universities(D5000210829);Fundamental Research Funds for the Central Universities(D5000210601)

Abstract

Abstract:

Clean and renewable energy is generally localized and intermittent. Thus, energy conversion and storage technologies are necessary to compensate for these shortcomings. Electrolytic water splitting presents a reliable and promising energy technology for producing high purity hydrogen (H₂). Among the platinum metals, ruthenium (Ru) has gained significant attentions as it generally outperforms commercial catalysts in terms of activity at a more affordable price. Although great progress has been made in improving the catalytic activity of Ru-based catalysts, stability remains a major challenge hindering their practical applications. To this end, this review introduces the fundamentals of the stability over Ru-based catalysts for water splitting, including the reaction mechanisms of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), measurement methods and evaluation criteria, as well as deactivation mechanisms. Moreover, the up-to-date advances of representative strategies for improving HER and OER stability of Ru-based catalysts are further discussed with respect to specific design principles and underlying mechanisms. Ultimately, insights into the challenges and opportunities for Ru-based electrocatalysts are provided to promote the development of next-generation Ru-based catalysts with exceptional stability. This review aims at guiding the design and synthesis of superior catalysts, generating increased interest among researchers, and stimulating further advanced research.

Key words: Electrocatalysis, Water splitting, Deactivation mechanism, Ruthenium-based catalyst, Stability

Wangyan Gou, Yichen Wang, Mingkai Zhang, Xiaohe Tan, Yuanyuan Ma, Yongquan Qu. A review on fundamentals for designing stable ruthenium-based catalysts for the hydrogen and oxygen evolution reactions[J]. Chinese Journal of Catalysis, 2024, 60: 68-106.

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Figures/Tables 33

Fig. 1. Schematic representation of substantial energy storage in valuable chemicals and fuels through water electrolysis.

Fig. 2. Representative milestone research work of Ru-based catalysts in HER and OER [40,41,43?-45,109,167,183,187,188]. Reprinted with permission from Ref. [40]. Copyright 1998, Elsevier. Reprinted with permission from Ref. [41]. Copyright 2018, John Wiley and Sons. Reprinted with permission from Ref. [43]. Copyright 2015, American Chemical Society. Reprinted with permission from Ref. [44]. Copyright 2016, Elsevier. Reprinted with permission from Ref. [45]. Copyright 2019, John Wiley and Sons. Reprinted with permission from Ref. [109]. Copyright 2017, Springer Nature. Reprinted with permission from Ref. [167]. Copyright 2023, Springer Nature. Reprinted with permission from Ref. [183]. Copyright 2020, Springer Nature. Reprinted with permission from Ref. [187]. Copyright 2021, Springer Nature. Reprinted with permission from Ref. [188]. Copyright 2023, Springer Nature.

Fig. 3. (a) Chemical processes in HER under acidic and alkaline conditions. (b) Relationship between the exchange current density (j0) and hydrogen adsorption free energy under the assumption of the Langmuir adsorption model. Reprinted with permission from Ref. [58]. Copyright 2022, John Wiley and Sons. (c) Volcano plot of the relationship between the exchange current density (j0) and the free energy of hydrogen adsorption (ΔGH*) for the surfaces of Ru and other metals. Reprinted with permission from Ref. [61]. Copyright 2021, Springer Nature.

Fig. 4. (a) Schematic illustration of the proposed AEM pathway of OER in alkaline media on an active metal site. (b-d) Schematic illustrations of three alternative pathways of LOM in alkaline media with different catalytic centers. (b) Oxygen-vacancy-site mechanism (OVSM). (c) Single-metal-site mechanism (SMSM). (d) Dual-metal-site mechanism (DMSM). Reprinted with permission from Ref. [65]. Copyright 2021, Royal Society of Chemistry.

Fig. 5. Degradation mechanisms of HER catalysts.

Table 1 Summary of representative Ru-based electrocatalysts toward HER.

Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	Stability			Ref.
Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	CA/retention (mA cm^-2@h@%)	CP/decay (mV@h@mV)	CV cycles/retention (cycles @%)	Ref.
Ru NRs/TiN	1.0 mol L^-1 KOH	25	27.08	—	~30@50@41	10000	[121]
Ru-NiCo₂S_4-_x	1.0 mol L^-1 KOH	32	61.3	20@12@100	—	1000	[147]
Ru SAs-SnO₂/C	1.0 mol L^-1 KOH	10	25	10@27@100	—	3000	[138]
Ru@MoO(S)₃	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	30/63	29/32	17@24@88	—	3000	[105]
Ru/TiO₂-V	1.0 mol L^-1 KOH	34	35.4	300@200@100 (80 °C and 6 mol L^-1 KOH)	—	—	[112]
RuFe@NF	1.0 mol L^-1 KOH	28	63.39	—	~310@680@0	—	[113]
Ru-G/CC	1.0 mol L^-1 KOH	40	76	8@100@100	—	—	[96]
Ru_xFe_yP-NCs/CNF	1.0 mol L^-1 NaOH/0.5 mol L^-1 H₂SO₄	16/66	40.31/43.33	~10@100@98	—	—	[100]
Ru SAs/N-Mo₂C NSs	1.0 mol L^-1 KOH	43	38.67	~22@60@93.7	—	—	[123]
RuO₂-NiO/NF	1.0 mol L^-1 KOH	18	27	20@100	—	—	[97]
NiRu-MOF/NF	1.0 mol L^-1 KOH	51	90	~30@24	~110@24@~40	5000	[98]
Ru‐NCs/N‐GA‐900	1.0 mol L^-1 KOH/1.0 mol L^-1 HClO₄	36/52	36.8	—	~150@40@50	10000	[99]
RuNP@RuN_x-OFC/NC	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	19/10	13.75/35.35	10@120@90	—	2000	[104]
R-NiRu	1.0 mol L^-1 KOH	16	40	~23@12@80	—	5000	[127]
2DPC-RuMo	1.0 mol L^-1 KOH	18	25	10@120@100	—	2000	[110]
P,Mo-Ru@PC	1.0 mol L^-1 KOH	21	21.7	10@10@100	—	5000	[111]
S-RuP@NPSC-900	1.0 mol L^-1 KOH	92	90.23	800@10@98	—	—	[107]
Ru-Ru₂P@CNFs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	14/11	24.5	6@11@83	—	3000	[108]
fcc-RuCu HUNSs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	26/25	40	—	25@5@25	—	[130]
MoO_x-Ru fcc	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	34/26	14.5	—	34@100@~16	—	[131]
Ru_Δc→h/C	0.5 mol L^-1 KOH	97 (50 mA cm^-2)	51	—	~45@12@5	5000	[132]
Ru_xSe-400	1.0 mol L^-1 KOH	45	31.4	10@18@80	—	3000	[135]
Ru/r-TiO₂	1.0 mol L^-1 KOH	15	49	10@10@~90	—	1000	[136]
RuO₂-300Ar	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	17/16	35	—	~220@300	—	[137]
Ru₁CoP/CDs-1000	1 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	51/49	73.4/51.6	10@20	—	2000	[146]
PtRu/mCNTs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄/1 mol L^-1 PBS	15/28/17	33.5	—	25@48	3000	[145]
Ru/p-NC	1.0 mol L^-1 KOH	10	17	14@24@93	—	3000	[144]
CNT-V-Fe-Ru	1.0 mol L^-1 KOH/0.5M H₂SO₄	38/64	41/51	—	64@20@11	—	[118]
Mo₂C-Ru/C	1.0 mol L^-1 KOH	22	25	10@100	—	—	[143]
Ru@Ti₃C₂T_x-V_C	1.0 mol L^-1 KOH	35	32	—	40@40@10	—	[142]
Ru@MWCNT	1 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	17/13	27/27	20@50	—	10000	[114]
Ru-Fe₃O₄/C	1.0 mol L^-1 KOH	11	25	56@32@95.5	—	5000	[141]
Cu-Ru/RuSe₂ NSs/C	1.0 mol L^-1 KOH	23	58.5	—	—	5000	[140]
Ru@N-CNFs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	17/16	28.5/31.8	15@17@80	—	2000	[101]
Ru/P-TiO₂	1.0 mol L^-1 KOH	27	28.3	9@23@78	—	2000	[139]
Ru-OC₆₀-300	1.0 mol L^-1 KOH	4.6	24.7	—	4.6@50@13.3	3000	[119]

Table 1 Summary of representative Ru-based electrocatalysts toward HER.

Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	Stability			Ref.
Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	CA/retention (mA cm^-2@h@%)	CP/decay (mV@h@mV)	CV cycles/retention (cycles @%)	Ref.
Ru NRs/TiN	1.0 mol L^-1 KOH	25	27.08	—	~30@50@41	10000	[121]
Ru-NiCo₂S_4-_x	1.0 mol L^-1 KOH	32	61.3	20@12@100	—	1000	[147]
Ru SAs-SnO₂/C	1.0 mol L^-1 KOH	10	25	10@27@100	—	3000	[138]
Ru@MoO(S)₃	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	30/63	29/32	17@24@88	—	3000	[105]
Ru/TiO₂-V	1.0 mol L^-1 KOH	34	35.4	300@200@100 (80 °C and 6 mol L^-1 KOH)	—	—	[112]
RuFe@NF	1.0 mol L^-1 KOH	28	63.39	—	~310@680@0	—	[113]
Ru-G/CC	1.0 mol L^-1 KOH	40	76	8@100@100	—	—	[96]
Ru_xFe_yP-NCs/CNF	1.0 mol L^-1 NaOH/0.5 mol L^-1 H₂SO₄	16/66	40.31/43.33	~10@100@98	—	—	[100]
Ru SAs/N-Mo₂C NSs	1.0 mol L^-1 KOH	43	38.67	~22@60@93.7	—	—	[123]
RuO₂-NiO/NF	1.0 mol L^-1 KOH	18	27	20@100	—	—	[97]
NiRu-MOF/NF	1.0 mol L^-1 KOH	51	90	~30@24	~110@24@~40	5000	[98]
Ru‐NCs/N‐GA‐900	1.0 mol L^-1 KOH/1.0 mol L^-1 HClO₄	36/52	36.8	—	~150@40@50	10000	[99]
RuNP@RuN_x-OFC/NC	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	19/10	13.75/35.35	10@120@90	—	2000	[104]
R-NiRu	1.0 mol L^-1 KOH	16	40	~23@12@80	—	5000	[127]
2DPC-RuMo	1.0 mol L^-1 KOH	18	25	10@120@100	—	2000	[110]
P,Mo-Ru@PC	1.0 mol L^-1 KOH	21	21.7	10@10@100	—	5000	[111]
S-RuP@NPSC-900	1.0 mol L^-1 KOH	92	90.23	800@10@98	—	—	[107]
Ru-Ru₂P@CNFs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	14/11	24.5	6@11@83	—	3000	[108]
fcc-RuCu HUNSs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	26/25	40	—	25@5@25	—	[130]
MoO_x-Ru fcc	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	34/26	14.5	—	34@100@~16	—	[131]
Ru_Δc→h/C	0.5 mol L^-1 KOH	97 (50 mA cm^-2)	51	—	~45@12@5	5000	[132]
Ru_xSe-400	1.0 mol L^-1 KOH	45	31.4	10@18@80	—	3000	[135]
Ru/r-TiO₂	1.0 mol L^-1 KOH	15	49	10@10@~90	—	1000	[136]
RuO₂-300Ar	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	17/16	35	—	~220@300	—	[137]
Ru₁CoP/CDs-1000	1 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	51/49	73.4/51.6	10@20	—	2000	[146]
PtRu/mCNTs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄/1 mol L^-1 PBS	15/28/17	33.5	—	25@48	3000	[145]
Ru/p-NC	1.0 mol L^-1 KOH	10	17	14@24@93	—	3000	[144]
CNT-V-Fe-Ru	1.0 mol L^-1 KOH/0.5M H₂SO₄	38/64	41/51	—	64@20@11	—	[118]
Mo₂C-Ru/C	1.0 mol L^-1 KOH	22	25	10@100	—	—	[143]
Ru@Ti₃C₂T_x-V_C	1.0 mol L^-1 KOH	35	32	—	40@40@10	—	[142]
Ru@MWCNT	1 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	17/13	27/27	20@50	—	10000	[114]
Ru-Fe₃O₄/C	1.0 mol L^-1 KOH	11	25	56@32@95.5	—	5000	[141]
Cu-Ru/RuSe₂ NSs/C	1.0 mol L^-1 KOH	23	58.5	—	—	5000	[140]
Ru@N-CNFs	1.0 mol L^-1 KOH/0.5 mol L^-1 H₂SO₄	17/16	28.5/31.8	15@17@80	—	2000	[101]
Ru/P-TiO₂	1.0 mol L^-1 KOH	27	28.3	9@23@78	—	2000	[139]
Ru-OC₆₀-300	1.0 mol L^-1 KOH	4.6	24.7	—	4.6@50@13.3	3000	[119]

Fig. 6. (a) Schematic illustration of synthesis of Ru-G/CC. (b) High resolution TEM (HRTEM) images of Ru-G/CC. (c) Comparison of the LSV curves of the initial electrode and the one after chronopotentiometry test for 100 h in 1.0 mol L?1 KOH. (d) Chronopotentiometry test performed at an overpotential of 270 mV for 100 h. (e) Calculated ΔG of H* on the surface of Ru-G/CC, Ru (101) and Pt (111). (f) Electron localized function of the adsorbed H-atom on the active sites. (g) Total DOS plots of amorphous/crystalline Ru structure. Reprinted with permission from Ref. [96]. Copyright 2022, Elsevier.

Fig. 7. (a) Schematic illustration of synthesis of RuxFeyP-NCs/CNF. (b) Field emission scanning electron microscopy (FESEM) image of RuFeP-NCs/CNF. (c) Chronoamperometry curves of RuFeP-NCs/CNF at an overpotential of 60 mV for 100 h in 0.5 mol L?1 H2SO4. (d) Polarization curves of RuFeP-NCs/CNF before and after 100 h stability tests. (e) Chronoamperometry curves of the RuFeP-NCs/CNF tested at an overpotential of 60 mV vs. RHE for 100 h in 1.0 mol L?1 NaOH solution. Calculated adsorption free energy of H* (ΔGH*) (f) and OH*+H* (ΔGOH*+H*) (g) for various catalysts. (h) Possible and optimized adsorption configurations of OH* and H* on RuFeP-NCs/CNF. Reprinted with permission from Ref. [100]. Copyright 2021, Elsevier.

Fig. 8. (a) Schematic illustration of synthesis of RuNP@RuNx-OFC/NC. (b) HRTEM image of RuNP@RuNx-OFC/NC. LSV curves of RuNP@RuNx-OFC/NC, RuNP-RuNx/NC and Pt/C in 0.5 mol L?1 H2SO4 (c) and 1.0 mol L?1 KOH (d). Long-term chronoamperometric test of RuNP@RuNx-OFC/NC in 0.5 mol L?1 H2SO4 (e) and 1.0 mol L?1 KOH (f) at a current density of 10 mA cm-2 (inset: the LSV curves of RuNP@RuNx-OFC/NC before (red) and after (black) 2000 CV cycles). (g) Optimized structure of RuNP@RuN4-FC and RuNP-RuN4/PC. Color code: Ru gold, N blue and C gray. (h) DOS diagram of RuNP@RuN4-FC and RuNP-RuN4/PC. (i) Relationship of ΔGH* against the d band center (εd) of the Ru atoms in RuNP@RuN4-FC and RuNP-RuN4/PC. Reprinted with permission from Ref. [104]. Copyright 2022, Elsevier.

Fig. 9. (a) Schematic illustration of the synthesis and structure of the Ru@C2N electrocatalyst. (b) TEM image of Ru@C2N (insets: corresponding particle size distribution of the Ru nanoparticles (bottom) and atomic-resolution TEM image (top)). (c) LSV curves of Ru@C2N, Co@C2N, Ni@C2N, Pd@C2N, Pt@C2N and Pt/C electrocatalysts in 0.5 mol L?1 H2SO4 solution. (d) Durability test. The LSV curves of Pt/C and Ru@C2N were recorded before and after 10000 potential cycles in 0.5 mol L?1 H2SO4 solution from 0.2 to -0.1 V (versus RHE). Reprinted with permission from Ref. [109]. Copyright 2017, Springer Nature. (e) A schematic fabrication procedure of metal-composite-embedded hexagonal porous carbon nanosheets. (f) Comparison of the LSV curve of the 2DPC-RuMo nanosheets electrocatalysts for the 1st and 2000th cycles (inset: long-term HER stability measurement at a constant overpotential of 20 mV (with IR correction)). (g) Calculated hydrogen-adsorption free energy profile for different models. Reprinted with permission from Ref. [110]. Copyright 2020, John Wiley and Sons. (h) Stability of Ru@TiO2-V, Ru/CNTs, and Ru/TiO2-V for HER in 6 mol L?1 KOH at 80 °C. (i) Schematic display the unchanged metal diameter of Ru NPs confined into the lattice framework of TiO2 and after stability test for enabling outstanding stability of HER and Ru NPs supported on the surface of TiO2 undergo aggregation and dissociation for enabling poor stability of HER under harsh conditions. Reprinted with permission from Ref. [112]. Copyright 2022, Elsevier.

Fig. 10. (a) Synthesis procedure for Ru-OC60-300. (b) Chronopotentiometry curve of Ru-OC60-300/KB and Pt/C at a constant current density of 10 mA cm-2. (c) Calculated ΔGH* of Ru13-O3-C60-top, Ru13-O3-C60-inter, Ru13-O3-G-top, and Ru13-O3-G-inter. (d) Charge differential density map of Ru13-O3-C60 and Ru13-O3-G. Cyan and yellow colors represent electron decrease and increase, respectively. (e) Energy diagram of Volmer-Tafel route for Ru13-O3-C60. Reprinted with permission from Ref. [119]. Copyright 2023, American Chemical Society. (f) Schematic synthesis processes and structure of Ru NRs/TiN catalyst. (g) LSV curves with before and after 10000 potential cycles of Ru NRs/TiN, Ru NRs/C and Pt/C in 1.0 mol L-1 KOH solution (inset: 50 h chronopotentiometry test). (h) Charge density difference of Ru/TiN. Cyan and yellow colors represent negative and positive isosurface, respectively. The value of the isosurface is 0.1 e bohr-3. (i) Calculated Gibbs free energy of atomic hydrogen adsorption on Ru/TiN, Ru (100), and Ru (-120) slabs. (j) Hydrogen adsorption configuration and the corresponding ΔGH* of Ru/TiN. Reprinted with permission from Ref. [121]. Copyright 2022, Elsevier.

Fig. 11. (a) Crystal models of the temperature-induced phase transformation. LSV curves (b) and Stability (c) of MoOx-Ru fcc, MoOx-Ru hcp, Ru/C and Pt/C in 1 mol L?1 KOH. (d) Distribution map of formation energy for metal Ru fcc phase and hcp phase in the condition of bulk, facets (fcc_111 and hcp_101, respectively), and MoOx modification. (e) Crystal orbital Hamilton population (COHP) curves for Ru-H adsorption bonds on Ru(111) surface in fcc phase and corresponding projected DOS diagram. The Fermi level is set at zero. Projected density of states (PDOS) of 4dz2 orbitals of Ru atoms on the surface of Ru without and with modification with MoOx, as well as the corresponding partial d-band center (εd) relative to the Fermi levels in fcc phase (f) and hcp phase (g), respectively. Gibbs free energy diagrams for the adsorption of H* (h) and OH* (i) on the surface of Ru without and with the modification of MoOx. Reprinted with permission from Ref. [131]. Copyright 2022, American Chemical Society.

Fig. 12. (a) A schematic diagram of phase-transition by atom slippage on the Ruccp(111) plane, in which the “A,” “B,” and “C” planes represented in light green, orange, and green. (b) The lattice distance of Ruccp(111) between the virtual horizontal line and Ruccp(111) (or Ruhcp(002)) orientation. (c) High-temperature XRD (HT-XRD) patterns of ccp/C heated to temperatures in the range of 200-500 °C under an Ar atmosphere. The black and red vertical lines representing the ccp (JCPDS# 88-2333) and hcp (JCPDS# 06-0663) Ru references. (d) Comparison of the LSV curve of the RuΔc→h/C electrocatalysts for the 1st and 5000th cycles (inset: HER stability measurement). (e) Schematic diagram describing different mechanisms of RuCX formation at RuΔc→h/C (top) and RuΔhcp/C (bottom). (f) Average H-binding free energy (ΔGH*) for each surface model. (g) Schematic diagram explaining the atomic-level bifunctional mechanism of the RuCX surface. Reprinted with permission from Ref. [132]. Copyright 2021, John Wiley and Sons.

Fig. 13. (a) Schematic illustration of the synthesis of Ru/r-TiO2 and Ru/TiO2 catalysts. (b) LSV curves of Ru/r-TiO2, Ru/TiO2, Pt/C, Ru/C, Ti(Ⅲ) oxide, TiO2 and GC electrocatalysts in 1.0 mol L?1 KOH solution. (c) Stability of Ru/r-TiO2 by 1000 potential cycles between -50 and 10 mV at 5 mV s-1 (inset: the stability of catalysts at a constant potential of 15 mV for 10 h). (d) Charge density differences for Ru(0001)/TiO2 (up) and Ru(0001)/r-TiO2 (down) interfaces. The yellow region represents charge accumulation, and the light blue region indicates charge depletion at the isosurface value of 0.01 e Bohr-3. (e) Free energy profiles for HER from water to H2 on different surfaces. (f) The enlarged view of OH*?adsorption on Ru(0001)/r-TiO2 and Ru(0001)/TiO2 interfaces. Green: Ru; grey: Ti; red: O; white: H. Reprinted with permission from Ref. [136]. Copyright 2021, Elsevier.

Fig. 14. (a) Schematic illustration of the synthesis of Ru SAs-SnO2/C. (b) LSV curves (iR compensated) of Ru SAs-SnO2/C, Ru/C, Pt/C, and SnO2/C electrocatalysts in 1.0 mol L-1 KOH at a scan rate of 5 mV s-1. (c) LSV curves of Ru SAs-SnO2/C electrocatalyst before and after 3000 CV cycles (inset: the chronoamperometry curve at -18 mV). (d) OH adsorption configurations on the Ru (001), Ru site on Ru SAs/SnO2 and Sn site on Ru SAs/SnO2, as well as corresponding binding energies. (e) Schematic showing of the mechanism of enhanced HER performance on Ru SAs-SnO2/C. Reprinted with permission from Ref. [138]. Copyright 2022, John Wiley and Sons.

Fig. 15. Timeline of investigations on the stability of Ru- based catalysts for HER.

Table 2 Summary of representative Ru-based electrocatalysts toward OER.

Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	Stability			Ref.
Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	CA/Retention (mA cm^-2@h@%)	CP/decay (mV@h@mV)	CV cycles/ retention (cycles @%)	Ref.
Ru/GDY	0.5 mol L^‒1 H₂SO₄	531	100	10@54@100	—	2000	[155]
YZRO/AB	0.5 mol L^‒1 H₂SO₄	291	36.9	—	290@6@~25	2000	[171]
PRPO-350	0.1 mol L^‒1 HClO₄	174	28.8	—	270@150@~63	2000	[175]
W_0.2Er_0.1Ru_0.7O_2-_δ	0.5 mol L^‒1 H₂SO₄	168	66.8	—	170@500@83	—	[183]
12Ru/MnO₂	0.1 mol L^‒1 HClO₄	161	29.4	—	161@200@169	—	[187]
Ru/NiFe²⁺Fe-LDH	1 mol L^‒1 KOH	194	36	—	290 (100 mA cm^-2)@100@16	—	[160]
RuO₂/D-TiO₂	0.5 mol L^‒1 H₂SO₄	180	43	—	270 (200 mA cm^-2)@100@16	—	[158]
YSRO-15	0.5 mol L^‒1 H₂SO₄	264	44.8	—	260@28	—	[172]
Ru@IrO_x	0.05 mol L^‒1 H₂SO₄	282	69.1	-@24@90	—	—	[148]
Ru SAs/AC-FeCoNi	1 mol L^‒1 KOH	205	40	10@48@100	—	—	[161]
S-RuFeO_x	0.1 mol L^‒1 HClO₄	187	40	—	170 (1 mA cm^-2)@50 @35	5000	[164]
RuMn	0.5 mol L^‒1 H₂SO₄	270	—	—	270@720@100	20000	[166]
Ru₁Ir₁O_x	0.5 mol L^‒1 H₂SO₄	204	71.3	—	270 (100 mA cm^-2)@110	1000	[149]
RuNi₂©G-250	0.5 mol L^‒1 H₂SO₄	227	65	—	270@24	—	[151]
Sr_1.7Ru₅Ir₁O_13.7	0.5 mol L^‒1 H₂SO₄	190	39	—	180@1500@43	—	[184]
PtCo-RuO₂/C	0.1 mol L^‒1 HClO₄	212.6	48.5	—	270@20@80	—	[185]
Sr_0.95Na_0.05RuO₃	0.1 mol L^‒1 HClO₄	160	—	—	—	20	[178]
Ru-N-C	0.5 mol L^‒1 H₂SO₄	267	52.6	11@30@95	—	1000	[156]
Ni-RuO₂	0.1 mol L^‒1 HClO₄	214	42.6	—	220@200	—	[167]
Re_0.06Ru_0.94O₂	0.1 mol L^‒1 HClO₄	190	45.5	—	190@200@50	—	[168]
Nb_0.1Ru_0.9O₂	0.5 mol L^‒1 H₂SO₄	204	47.9	—	770 (200 mA cm^-2)@360	—	[169]
RuIr-NC	0.05 mol L^‒1 H₂SO₄	165	—	—	165 (1 mA cm^-2)@122	—	[150]
Ru₅W₁O_x	0.5 mol L^‒1 H₂SO₄	235	—	—	235@550	10000	[186]
Y₂Ru_2-_xIr_xO₇	0.1 mol L^‒1 HClO₄	220	47.56	—	500@2000	—	[176]
CaCu₃Ru₄O₁₂	0.5 mol L^‒1 H₂SO₄	171	40	—	171@24@21	—	[179]
Cr_0.6Ru_0.4O₂	0.5 mol L^‒1 H₂SO₄	178	58	—	178@10	10000	[163]
RuMn NSBs-300	0.5 mol L^‒1 H₂SO₄/1 mol L^‒1 KOH	226/222	—	—	230@122	—	[165]
RuRh@(RuRh)O₂	0.1 mol L^‒1 HClO₄	245	51.2	—	270@2.22	—	[153]
Ni-Ru@RuO_x-HL	0.5 mol L^‒1 H₂SO₄	184	54	—	184@30	—	[154]
Au@Pt@RuO_x	0.1 mol L^‒1 HClO₄	215	60.1	—	220@40	—	[189]
RuOCl@MnO_x	0.5 mol L^‒1 H₂SO₄	228	43	—	228@280@50	—	[190]
a/c-RuO₂	0.1 mol L^‒1 HClO₄	205	48.6	—	240@60	—	[191]
HRO	0.1 mol L^‒1 HClO₄	215	36.86	—	270 (1 mA cm^-2)@60	1000	[173]
CaCu₃Ru₄O₁₂	1 mol L^‒1 H₂SO₄	320	59	—	—	100	[180]
RuIr@CoNC	0.5 mol L^‒1 H₂SO₄	223	45	—	230@40@90	—	[157]
NC@Vo·-RuO₂/CNTs-350	0.5 mol L^‒1 H₂SO₄	170	38.9	—	170@900	2000	[152]
Y₂MnRuO₇	0.5 mol L^‒1 H₂SO₄	260	48	—	270@45	2000	[177]

Table 2 Summary of representative Ru-based electrocatalysts toward OER.

Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	Stability			Ref.
Catalyst	Electrolyte	η₁₀ (mV)	Tafel slope (mV dec^-1)	CA/Retention (mA cm^-2@h@%)	CP/decay (mV@h@mV)	CV cycles/ retention (cycles @%)	Ref.
Ru/GDY	0.5 mol L^‒1 H₂SO₄	531	100	10@54@100	—	2000	[155]
YZRO/AB	0.5 mol L^‒1 H₂SO₄	291	36.9	—	290@6@~25	2000	[171]
PRPO-350	0.1 mol L^‒1 HClO₄	174	28.8	—	270@150@~63	2000	[175]
W_0.2Er_0.1Ru_0.7O_2-_δ	0.5 mol L^‒1 H₂SO₄	168	66.8	—	170@500@83	—	[183]
12Ru/MnO₂	0.1 mol L^‒1 HClO₄	161	29.4	—	161@200@169	—	[187]
Ru/NiFe²⁺Fe-LDH	1 mol L^‒1 KOH	194	36	—	290 (100 mA cm^-2)@100@16	—	[160]
RuO₂/D-TiO₂	0.5 mol L^‒1 H₂SO₄	180	43	—	270 (200 mA cm^-2)@100@16	—	[158]
YSRO-15	0.5 mol L^‒1 H₂SO₄	264	44.8	—	260@28	—	[172]
Ru@IrO_x	0.05 mol L^‒1 H₂SO₄	282	69.1	-@24@90	—	—	[148]
Ru SAs/AC-FeCoNi	1 mol L^‒1 KOH	205	40	10@48@100	—	—	[161]
S-RuFeO_x	0.1 mol L^‒1 HClO₄	187	40	—	170 (1 mA cm^-2)@50 @35	5000	[164]
RuMn	0.5 mol L^‒1 H₂SO₄	270	—	—	270@720@100	20000	[166]
Ru₁Ir₁O_x	0.5 mol L^‒1 H₂SO₄	204	71.3	—	270 (100 mA cm^-2)@110	1000	[149]
RuNi₂©G-250	0.5 mol L^‒1 H₂SO₄	227	65	—	270@24	—	[151]
Sr_1.7Ru₅Ir₁O_13.7	0.5 mol L^‒1 H₂SO₄	190	39	—	180@1500@43	—	[184]
PtCo-RuO₂/C	0.1 mol L^‒1 HClO₄	212.6	48.5	—	270@20@80	—	[185]
Sr_0.95Na_0.05RuO₃	0.1 mol L^‒1 HClO₄	160	—	—	—	20	[178]
Ru-N-C	0.5 mol L^‒1 H₂SO₄	267	52.6	11@30@95	—	1000	[156]
Ni-RuO₂	0.1 mol L^‒1 HClO₄	214	42.6	—	220@200	—	[167]
Re_0.06Ru_0.94O₂	0.1 mol L^‒1 HClO₄	190	45.5	—	190@200@50	—	[168]
Nb_0.1Ru_0.9O₂	0.5 mol L^‒1 H₂SO₄	204	47.9	—	770 (200 mA cm^-2)@360	—	[169]
RuIr-NC	0.05 mol L^‒1 H₂SO₄	165	—	—	165 (1 mA cm^-2)@122	—	[150]
Ru₅W₁O_x	0.5 mol L^‒1 H₂SO₄	235	—	—	235@550	10000	[186]
Y₂Ru_2-_xIr_xO₇	0.1 mol L^‒1 HClO₄	220	47.56	—	500@2000	—	[176]
CaCu₃Ru₄O₁₂	0.5 mol L^‒1 H₂SO₄	171	40	—	171@24@21	—	[179]
Cr_0.6Ru_0.4O₂	0.5 mol L^‒1 H₂SO₄	178	58	—	178@10	10000	[163]
RuMn NSBs-300	0.5 mol L^‒1 H₂SO₄/1 mol L^‒1 KOH	226/222	—	—	230@122	—	[165]
RuRh@(RuRh)O₂	0.1 mol L^‒1 HClO₄	245	51.2	—	270@2.22	—	[153]
Ni-Ru@RuO_x-HL	0.5 mol L^‒1 H₂SO₄	184	54	—	184@30	—	[154]
Au@Pt@RuO_x	0.1 mol L^‒1 HClO₄	215	60.1	—	220@40	—	[189]
RuOCl@MnO_x	0.5 mol L^‒1 H₂SO₄	228	43	—	228@280@50	—	[190]
a/c-RuO₂	0.1 mol L^‒1 HClO₄	205	48.6	—	240@60	—	[191]
HRO	0.1 mol L^‒1 HClO₄	215	36.86	—	270 (1 mA cm^-2)@60	1000	[173]
CaCu₃Ru₄O₁₂	1 mol L^‒1 H₂SO₄	320	59	—	—	100	[180]
RuIr@CoNC	0.5 mol L^‒1 H₂SO₄	223	45	—	230@40@90	—	[157]
NC@Vo·-RuO₂/CNTs-350	0.5 mol L^‒1 H₂SO₄	170	38.9	—	170@900	2000	[152]
Y₂MnRuO₇	0.5 mol L^‒1 H₂SO₄	260	48	—	270@45	2000	[177]

Fig. 16. (a) Schematic illustration of the synthetic procedures of catalysts. (b) LSV curves of various electrocatalysts (C-RuO2, C-IrO2, and Ir/C represent the commercial RuO2, IrO2, and Ir/C, respectively). (c) Chronopotentiometry curves of Ru1Ir1Ox. (d) S-number for various electrocatalysts at 10 mA cm-2geo. (e) The DOS curves of IrOx, RuOx, and Ru1Ir1Ox. (f) Charge density difference of IrOx and Ru1Ir1Ox (Blue and yellow colors represent charge depletion and accumulation, respectively). (g) The Gibbs free energy diagram of IrOx, RuOx, and Ru1Ir1Ox. Reprinted with permission from Ref. [149]. Copyright 2021, John Wiley and Sons.

Fig. 17. (a) Schematic illustration of the synthetic process of RuNi2?G-250. “T” represents the different oxidation temperatures, and “X” represents the molar ratios of Ru and Ni precursors. (b) LSV curves of RuNi2?G-250 in comparison with other catalysts treated at different oxidation temperatures and commercial RuO2 at the same mass loading of 0.32 mg cm-2. (c) Chronopotentiometric curve of RuNi2?G-250 supported on carbon fibers at a mass loading of 3 mg cm-2. (d) X-ray absorption near-edge structure (XANES) of Ru K-edge for RuNi2?G-250 supported on carbon fibers before and after 24 h stability testing. (e) The catalytical reaction circle and the active sites for interface Ru centers. The red, gray, white, and blue balls represent O, C, H, and Ru atoms, respectively. (f) The calculated overpotential (η) against the free energy of O* (ΔGO*) and HOO* (ΔGHOO*) on different active sites: a pristine RuO2 site, interface Ru centers, a Ru site under graphene or graphene oxide, and a Ru site adjacent to Ni (Ru adjacent to Ni); P1-P4 represent the graphene with different degrees of oxidation, and d1.5-d3.0 represent the different heights between graphene and RuO2. (g) Free energy profiles for the OER over RuO2 and interfacial Ru centers between RuO2 and graphene with an armchair edge at zero potential (U = 0). (h) Differential charge density at the interfacial Ru centers between RuO2 and graphene. Yellow and blue contours represent electron accumulation and depletion, respectively. The isovalue is set to be 0.004 a.u. Reprinted with permission from Ref. [151]. Copyright 2020, John Wiley and Sons.

Fig. 18. (a) SEM image of RuIr@CoNC catalysts. (b) CP curves of RuIr@CoNC recorded at a constant current density of 10 mA cm-2 in 0.5 mol L?1 H2SO4, 0.05 mol L?1 H2SO4, and PBS. (c) ICP-OES analysis of the dissolution of Ru, Ir, and Co of RuIr@CoNC during the OER electrolysis after different time intervals in 0.5 mol L?1 H2SO4. (d) Gibbs free-energy diagram on the flat and step surfaces, calculated at 1.23 V. (e) The Bader charge analysis of the flat and step surfaces. The green, blue, and red spheres represent Ru, Ir, and O atoms, respectively. (f) Calculated PDOS of Ru d-band on the flat and step surfaces. The dotted lines denote the d-band center. Reprinted with permission from Ref. [157]. Copyright 2021, American Chemical Society. (g) High-resolution TEM of RuO2/D-TiO2 (inset: a structural schematic for the composite catalyst). (h) Electron paramagnetic resonance (EPR) spectra of RuO2/D-TiO2, RuO2/C, and RuO2/TiO2. (i) CP measurements with different applied current densities. (j) Long-term stability tests at a constant current density of 200 mA cm-2 in a three-electrode electrolyzer. (k) Limiting potential diagram for AEM and LOM on model surfaces. Reprinted with permission from Ref. [158]. Copyright 2022, American Chemical Society.

Fig. 19. (a) Synthetic scheme of the Ru-UiO-67-bpydc catalyst (bpydc represents 2,2'-bipyridine-5,5'-dicarboxylic acid). (b) Initial LSV curves of Ru-UiO-67-bpydc and the LSV curves of catalysts after 1000 CV cycles. (c) Chronopotentiometric curves of Ru-UiO-67-bpydc at a current density of 10/50 mA cm-2 and RuO2 at a current density of 10 mA cm-2. (d) Crystal orbital Hamilton population of Ru-N and Ru-OOH bond in Ru-UiO-67-bpydc and -COHP of Ru-O and Ru-OOH in RuO2 catalysts. (e) Gibbs free energy illustration by Ru-UiO-67-bpydc and RuO2 catalysts during the OER process through the AEM or LOM pathways. (f) The transformation of RuO2 to RuO42- during the acidic OER process via the LOM pathway. (g) The stability of the Ru intermediate in the MOF-anchored Ru oxide during the acidic OER through the LOM pathway. Reprinted with permission from Ref. [162]. Copyright 2023, Elsevier.

Fig. 20. (a) LSV curves of RuMn NSBs with a 85% iR-correction after 1000, 5000, 10000, and 20000 cycles (inset: the overpotential at 10 mA cm-2). (b) Ru and Mn dissolution. (c) The chronopotentiometry curve of RuMn NSBs and commercial RuO2 at 10 mA cm-2. (d) Schematic of surface reconstruction of RuMn NSBs and dissolution of unstable Ru-based alloys in acidic media during CV cycles. (e) Durability-binding energy (Ru) relationships found in this study. Reprinted with permission from Ref. [166]. Copyright 2022, John Wiley and Sons.

Fig. 21. (a) Schematic illustration of the synthesis of Ni-RuO2. (b) LSV curves of Ni-RuO2, RuO2 and Com-RuO2. (c) Stability tests of Ni-RuO2, RuO2 and Com-RuO2. (d) Calculated free energy of OER via AEM on surfaces of RuO2 (110) and Ni-RuO2 (110) under an electrode potential of 1.70?V. (e) Calculated energies for the structural degradation of the surfaces of RuO2 (110) and Ni-RuO2 (110). Reprinted with permission from Ref. [167]. Copyright 2023, Springer Nature.

Fig. 22. (a) Chronopotentiometry curves of YSRO-15 and RuO2 catalysts at a current density of 10 mA cmgeo-2. (b) Surface and bulk atomic percentages of the YSRO-15 catalyst after the stability test, observed from in-depth XPS spectra. (c) Schematic illustrations of different RuO6 along with the splitting of Ru 4d orbitals. (d) PDOS diagrams of Ru 4d and O 2p orbitals in pristine Y2Ru2O7 (top) and the 12.5 at% Sr-substituted Y1.75Sr0.25Ru2O7 (bottom) model. Calculated free energy diagrams of the OER pathway for the Y2Ru2O7 (e) and Y1.75Sr0.25Ru2O7 (f) models. Reprinted with permission from Ref. [172]. Copyright 2021, American Chemical Society.

Fig. 23. (a) Crystalline structure of Y2Ru2O7 with Ir doping. (b) LSV curves (inset: LSV curves of pyrochlores with different Ru/Ir ratios). (c) Chronpotentionary measurement of Y2Ru1.2Ir0.8O7 and commercial RuO2 at 10 mA cm-2 respectively. (d) Adsorption of oxygen intermediates at Ir site. (e) Free energy diagram of Ru in Y2Ru1.2Ir0.8O7 and RuO2. (f) Free energy diagram of Ir in Y2Ru1.2Ir0.8O7 and IrO2. Reprinted with permission from Ref. [176]. Copyright 2022, John Wiley and Sons.

Fig. 24. (a) Schematic route for synthesis of W0.2Er0.1Ru0.7O2-δ nanosheets. (b) Extended X-ray absorption fine structure (EXAFS) spectra of Ru K-edge for Ru foil, C-RuO2, W0.2Er0.1Ru0.7O2-δ, and RuO2?δ. (c) LSV curves of W0.2Er0.1Ru0.7O2-δ, Er0.1Ru0.9O2-δ, W0.2Ru0.8O2-δ, and RuO2-δ nanosheets. (d) Stability of W0.2Er0.1Ru0.7O2-δ nanosheets in 0.5 mol L-1 H2SO4. (e) ICP analysis of the spent W0.2Er0.1Ru0.7O2-δ catalysts after 500 h operation in acid. (f) Schematic diagrams of rigid band models for RuO2 and W0.2Er0.1Ru0.7O2-δ-1 in acidic OER. (g) Calculated energy for the formation of VO in different positions of RuO2, W0.2Ru0.8O2-δ-1, Er0.1Ru0.9O2-δ-1, and W0.2Er0.1Ru0.7O2-δ-1. (h) Calculated energy barriers diagram of W0.2Er0.1Ru0.7O2-δ-1. Reprinted with permission from Ref. [183]. Copyright 2020, Springer Nature.

Fig. 25. (a) Normalized LSV curves of MRuOx based on geometric areas. (b) Chronopotentiometry curve of SnRuOx operated at 100 mA cm-2 during the 250-h test. (c) DEMS signals of 32O2, 34O2 and 36O2 from the reaction products of MRu16Ox in H18O aqueous sulfuric acid electrolyte. The right part presented the variation of 16O: 18O ratio with Ru oxidation states of MRuOx. (d) The variation of apparent overpotential at 10 mA cm-2 with Ru oxidation states. (e) The variation trend of Ru K-edge absorption energy (E0) of SnRuOx and RuOx under different potentials. (f) Summary of the Ru-O bond length of SnRuOx and RuOx under various potentials. (g) The variation of It2g-p/Ieg-p with applied potentials for SnRuOx and RuOx. Reprinted with permission from Ref. [187]. Copyright 2023, Springer Nature.

Fig. 26. (a) Schematic illustration of the simplified OPM mechanism. (b) Electrocatalytic OER performance of MnO2, Ru/MnO2 and homemade RuO2 in 0.1 mol L?1 HClO4. (c) Chronopotentiometric response of the 12Ru/MnO2 catalyst in an H-type cell (inset photo) using carbon cloth as a current collector (inset: the chronopotentiometric response of 12Ru/MnO2 and RuO2 using gassy carbon as the current collector). Operando synchrotron FTIR spectra recorded in the potential range of 1.2-1.6 V versus RHE for 12Ru/MnO2 (d) and commercial RuO2 (e). (f) DEMS signals of O2 products for 12Ru/MnO2 in the electrolyte using H218O as the solvent during three times of LSV in the potential range of 1.17-1.72 V versus RHE, with a 10 mV s-1 scan rate. Reprinted with permission from Ref. [188]. Copyright 2021, Springer Nature.

Fig. 27. Timeline for investigations on the stability of Ru-based catalysts for OER.

Table 3 Summary of representative Ru-based electrocatalysts toward water splitting.

Catalyst	Electrolyte	Potential (V@mA cm^-2)	Stability (h)	Ref.
Ru-G/CC	1.0 mol L^‒1 KOH	1.67@10	—	[96]
Ru-NiCo₂S₄	1.0 mol L^‒1 KOH	1.46@10	24	[147]
Ru SAs-SnO₂/C	1.0 mol L^‒1 KOH	1.49@10	27	[138]
Ru@MoO(S)₃	1.0 mol L^‒1 KOH/0.5 mol L^‒1 H₂SO₄	1.526@10/1.522@10	24/24	[105]
RuFe@NF	1.0 mol L^‒1 KOH	1.54@10	680	[113]
Ru_xFe_yP-NCs/CNF	1.0 mol L^‒1 NaOH	1.6@10	10	[100]
RuO₂-NiO/NF	1.0 mol L^‒1 KOH	1.43@10	2000	[97]
RuNP@RuN_x-OFC/NC	1.0 mol L^‒1 KOH	1.337@10/1.615@100	50	[104]
Ru-WO₃	1.0 mol L^‒1 KOH	1.86@1000	100	[128]
RuO₂-300Ar	1.0 mol L^‒1 KOH/0.5 mol L^‒1 H₂SO₄	1.45@10/1.54@100	300/300	[137]
a/c-RuO₂	0.5 mol L^‒1 H₂SO₄	1.5210@10	20	[191]
SrRuIr	0.5 mol L^‒1 H₂SO₄	1.5@1000	150	[184]
Nb_0.1Ru_0.9O₂	0.5 mol L^‒1 H₂SO₄	1.69@1000	100	[169]
Nd_0.1RuO_x/CC	0.5 mol L^‒1 H₂SO₄	1.455@10	50	[170]
Ni-RuO₂	0.1 mol L^‒1 HClO₄	1.78@500	1000	[167]
PRPO-350	0.1 mol L^‒1 HClO₄	1.8@1140	—	[175]
PtCo-RuO₂/C	0.1 mol L^‒1 HClO₄	2.0@4400	24	[185]
RuO₂/D-TiO₂	0.5 mol L^‒1 H₂SO₄	1.74@1500	6	[158]
Y₂Ru_2-_xIr_xO₇	0.1 mol L^‒1 HClO₄	1.645@100	150	[176]
SnRuO_x	0.5 mol L^‒1 H₂SO₄	1.565@1000	1300	[186]
RuIr-NC	0.05 mol L^‒1 H₂SO₄	1.485@10	120	[150]
RuMn NSBs-300	1.0 mol L^‒1 KOH/0.5 mol L^‒1 H₂SO₄	1.452@10/1.456@10	125	[165]
YZRO/AB	0.5 mol L^‒1 H₂SO₄	1.65@340	—	[171]
NC@Vo·-RuO₂/CNTs-350	0.5 mol L^‒1 H₂SO₄	1.45@10	1000	[152]
Ru_0.85Zn_0.15O_2-_δ	1.0 mol L^‒1 KOH/0.5 mol L^‒1 H₂SO₄	1.47@10/1.50@10	50	[163]
Y₂MnRuO₇	0.1 mol L^‒1 HClO₄	1.75@1000	24	[177]

Fig. 28. (a) Polarization curves of a/c-RuO2||c-RuO2 and commercial Pt/C||RuO2 for water splitting in 0.5 mol L?1 H2SO4. (b) Photo image of a/c-RuO2-based two-electrode electrolyzer driven by a battery with 1.5 V. (c) Time-dependent current density curves of a/c-RuO2||a/c-RuO2 and commercial Pt/C||RuO2 for water splitting in 0.5 mol L?1 H2SO4 at 50 mA cm-2. Reprinted with permission from Ref. [191]. Copyright 2021, John Wiley and Sons. (d) Polarization curves of the catalysts in the two-electrode configuration for water splitting. (e) Photo of the RuO2-NiO/NF||RuO2-NiO/NF couple powered by a single AA battery. (f) Chronoamperometric curves of RuO2-NiO/NF||RuO2-NiO/NF. Reprinted with permission from Ref. [97]. Copyright 2020, Royal Society of Chemistry. (g) Schematic diagram of the PEM electrolyzer. Reprinted with permission from Ref. [170]. Copyright 2023, John Wiley and Sons. (h) Steady-state polarization curve of a PEM electrolyzer measured at 80 °C using SrRuIr as anodic catalysts. (i) Chronopotentiometry tests of the SrRuIr oxide catalyst at 1 A cm?2 in the PEM electrolyzer measured at 80 °C. Reprinted with permission from Ref. [184]. Copyright 2021, American Chemical Society.

Fig. 29. Illustration of fundamentals and strategies to improve the stability of Ru-based catalysts in HER and OER.

Fig. 30. Schematic illustration of potential research issues related to the catalytic stability of Ru-based catalysts.

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A review on fundamentals for designing stable ruthenium-based catalysts for the hydrogen and oxygen evolution reactions

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