Synthetic tuning stabilizes a high-valence ru single site for efficient electrolysis

ABSTRACT Water electrolysis powered by renewable electricity can produce clean hydrogen, but the technology is limited by the slow anodic oxygen evolution reaction (OER). The most active

monometallic OER catalyst is high-valence ruthenium, but it is thermodynamically unstable. Here we leverage the strong and tunable interaction between substrate and active site found in

single atom catalysts, and discover a local electronic manipulation strategy for stabilizing high-valence Ru single sites (Ru SS) on a class of Ni-based phosphate porous hollow spheres (Ru

SS MNiPi PHSs where M = Fe, Co, Mn, Cu) for efficient electrolysis. Both X-ray absorption fine structure and density functional theory calculation results verify the intrinsic stability of

the catalyst, and suggest that this originates from the tailored valence state, coordination number and local electronic structure of the Ru SS. We formulate general guidelines for

stabilizing high-valence catalytic sites and introduce a double-volcano plot to describe the superior electrocatalytic behaviours of high-valence Ru SS. The optimum Ru SS/FeNiPi achieves a

low overpotential of 204 mV and 49 mV for the OER and hydrogen evolution reaction at 10 mA cm−2, respectively. Assembling Ru SS/FeNiPi in an industrial-level electrolyser with a low Ru

loading of 0.081 mg cm−2 realizes a stable industrial current density of 2,000 mA cm−2 at 1.78 V, which is the highest reported value in alkaline electrolyte to the best of our knowledge,

and exceeds that of commercial Pt//RuO2 by 5.7 times. Access through your institution Buy or subscribe This is a preview of subscription content, access via your institution ACCESS OPTIONS

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institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS PINNING EFFECT OF LATTICE PB SUPPRESSING LATTICE OXYGEN REACTIVITY OF PB-RUO2

ENABLES STABLE INDUSTRIAL-LEVEL ELECTROLYSIS Article Open access 12 November 2024 BICONTINUOUS RUO2 NANOREACTORS FOR ACIDIC WATER OXIDATION Article Open access 09 May 2024 STRONG-WEAK DUAL

INTERFACE ENGINEERED ELECTROCATALYST FOR LARGE CURRENT DENSITY HYDROGEN EVOLUTION REACTION Article Open access 18 January 2025 DATA AVAILABILITY The data supporting the findings of this

study are available within the article and its Supplementary Information. REFERENCES * Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design.

_Science_ 355, eaad4998 (2017). Article  PubMed  Google Scholar  * Hwang, J. et al. Perovskites in catalysis and electrocatalysis. _Science_ 358, 751–756 (2017). Article  CAS  PubMed  Google

Scholar  * Xia, B. Y. et al. A metal–organic framework-derived bifunctional oxygen electrocatalyst. _Nat. Energy_ 1, 1–8 (2016). Article  Google Scholar  * Reier, T., Nong, H. N., Teschner,

D., Schlögl, R. & Strasser, P. Electrocatalytic oxygen evolution reaction in acidic environments—reaction mechanisms and catalysts. _Adv. Energy Mater._ 7, 1601275 (2017). Article 

Google Scholar  * Vojvodic, A. & Nørskov, J. K. Optimizing perovskites for the water-splitting reaction. _Science_ 334, 1355–1356 (2011). Article  CAS  PubMed  Google Scholar  * Grimaud,

A. et al. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. _Nat. Chem._ 9, 457–465 (2017). Article  CAS  PubMed  Google Scholar  * Cheng, F. et al.

Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts. _Nat. Chem._ 3, 79–84 (2011). Article  CAS  PubMed  Google Scholar  * Bu, L.

et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. _Science_ 354, 1410–1414 (2016). Article  CAS  PubMed  Google Scholar  * Luo, M. et al. PdMo

bimetallene for oxygen reduction catalysis. _Nature_ 574, 81–85 (2019). Article  CAS  PubMed  Google Scholar  * Li, Y. et al. Recent advances on water‐splitting electrocatalysis mediated by

noble‐metal‐based nanostructured materials. _Adv. Energy Mater._ 10, 1903120 (2020). Article  CAS  Google Scholar  * Li, M. et al. Exclusive strain effect boosts overall water splitting in

PdCu/Ir core/shell nanocrystals. _Angew. Chem. Int. Ed._ 60, 8243–8250 (2021). Article  CAS  Google Scholar  * Greeley, J. & Mavrikakis, M. Alloy catalysts designed from first

principles. _Nat. Mater._ 3, 810–815 (2004). Article  CAS  PubMed  Google Scholar  * Mahmood, J. et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution

reaction. _Nat. Nanotechnol._ 12, 441–446 (2017). Article  CAS  PubMed  Google Scholar  * Stoerzinger, K. A. et al. The role of Ru redox in pH-dependent oxygen evolution on rutile ruthenium

dioxide surfaces. _Chem_ 2, 668–675 (2017). Article  CAS  Google Scholar  * Zheng, X. et al. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft

X-ray absorption. _Nat. Chem._ 10, 149 (2018). Article  CAS  PubMed  Google Scholar  * Shan, J. et al. Charge-redistribution-enhanced nanocrystalline Ru@ IrO_x_ electrocatalysts for oxygen

evolution in acidic media. _Chem_ 5, 445–459 (2019). Article  CAS  Google Scholar  * Cao, L. et al. Dynamic oxygen adsorption on single-atomic Ruthenium catalyst with high performance for

acidic oxygen evolution reaction. _Nat. Commun._ 10, 1–9 (2019). Article  Google Scholar  * Muthukumaran, S. & Gopalakrishnan, R. Structural, FTIR and photoluminescence studies of Cu

doped ZnO nanopowders by co-precipitation method. _Opt. Mater._ 34, 1946–1953 (2012). Article  CAS  Google Scholar  * Zhai, T. et al. Phosphate ion functionalized Co3O4 ultrathin nanosheets

with greatly improved surface reactivity for high performance pseudocapacitors. _Adv. Mater_. 29, 1604167 (2017). * Lasia, A. in _Modern Aspects of Electrochemistry_ 1–49 (Springer New York,

2002). * Hansen, J. N. et al. Is there anything better than Pt for HER? _ACS Energy Lett._ 6, 1175–1180 (2021). Article  CAS  PubMed  PubMed Central  Google Scholar  * Lu, S.-Y., Li, S.,

Jin, M., Gao, J. & Zhang, Y. Greatly boosting electrochemical hydrogen evolution reaction over Ni3S2 nanosheets rationally decorated by Ni3Sn2S2 quantum dots. _Appl. Catal. B_ 267,

118675 (2020). * Du, H. et al. Engineering morphologies of cobalt pyrophosphates nanostructures toward greatly enhanced electrocatalytic performance of oxygen evolution reaction. _Small_ 14,

1801068 (2018). Article  Google Scholar  * Rinke, M. T. & Eckert, H. The mixed network former effect in glasses: solid state NMR and XPS structural studies of the glass system (Na2O)_x_

(BPO4)1−_x_. _Phys. Chem. Chem. Phys._ 13, 6552–6565 (2011). Article  CAS  PubMed  Google Scholar  * Hu, Y. et al. Single Ru atoms stabilized by hybrid amorphous/crystalline FeCoNi layered

double hydroxide for ultraefficient oxygen evolution. _Adv. Energy Mater._ 11, 2002816 (2021). Article  CAS  Google Scholar  * Zhou, P. et al. Atomically dispersed Co–P3 on CdS nanorods with

electron‐rich feature boosts photocatalysis. _Adv. Mater._ 32, 1904249 (2020). Article  CAS  Google Scholar  * Yao, Y. et al. Engineering the electronic structure of single atom Ru sites

via compressive strain boosts acidic water oxidation electrocatalysis. _Nat. Catal._ 2, 304–313 (2019). Article  CAS  Google Scholar  * Lu, B. et al. Ruthenium atomically dispersed in carbon

outperforms platinum toward hydrogen evolution in alkaline media. _Nat. Commun._ 10, 1–11 (2019). Google Scholar  * Sun, Y. et al. Modulating electronic structure of metal–organic

frameworks by introducing atomically dispersed Ru for efficient hydrogen evolution. _Nat. Commun._ 12, 1–8 (2021). Google Scholar  * Yu, H. et al. 2D graphdiyne loading ruthenium atoms for

high efficiency water splitting. _Nano Energy_ 72, 104667 (2020). Article  CAS  Google Scholar  * Chen, Z. et al. TM LDH meets birnessite: a 2D–2D hybrid catalyst with long‐term stability

for water oxidation at industrial operating conditions. _Angew. Chem._ 133, 9785–9791 (2021). Article  Google Scholar  * Yin, J. et al. Iridium single atoms coupling with oxygen vacancies

boosts oxygen evolution reaction in acid media. _J. Am. Chem. Soc._ 142, 18378–18386 (2020). Article  CAS  PubMed  Google Scholar  * Li, P. et al. Boosting oxygen evolution of single-atomic

ruthenium through electronic coupling with cobalt-iron layered double hydroxides. _Nat. Commun._ 10, 1711 (2019). Article  PubMed  PubMed Central  Google Scholar  * Lu, S. Y. et al.

Chemically exfoliating biomass into a graphene‐like porous active carbon with rational pore structure, good conductivity, and large surface area for high‐performance supercapacitors. _Adv.

Energy Mater._ 8, 1702545 (2018). Article  Google Scholar  * Clark, S. J. et al. First principles methods using CASTEP. _Z. Kristallogr._ 220, 567–570 (2005). Article  CAS  Google Scholar  *

Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. _Phys. Rev. Lett._ 77, 3865–3868 (1996). Article  CAS  PubMed  Google Scholar  * Hasnip, P. J.

& Pickard, C. J. Electronic energy minimisation with ultrasoft pseudopotentials. _Comput. Phys. Commun._ 174, 24–29 (2006). Article  CAS  Google Scholar  * Perdew, J. P. et al. Atoms,

molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. _Phys. Rev. B_ 46, 6671–6687 (1992). Article  CAS  Google Scholar  *

Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. _Phys. Rev. B_ 41, 7892–7895 (1990). Article  CAS  Google Scholar  * Louie, S. G., Froyen, S.

& Cohen, M. L. Nonlinear ionic pseudopotentials in spin-density-functional calculations. _Phys. Rev. B_ 26, 1738–1742 (1982). Article  CAS  Google Scholar  * Grinberg, I., Ramer, N. J.

& Rappe, A. M. Transferable relativistic Dirac–Slater pseudopotentials. _Phys. Rev. B_ 62, 2311–2314 (2000). Article  CAS  Google Scholar  * Head, J. D. & Zerner, M. C. A

Broyden–Fletcher–Goldfarb–Shanno optimization procedure for molecular geometries. _Chem. Phys. Lett._ 122, 264–270 (1985). Article  CAS  Google Scholar  * Probert, M. I. J. & Payne, M.

C. Improving the convergence of defect calculations in supercells: an ab initio study of the neutral silicon vacancy. _Phys. Rev. B_ 67, 075204 (2003). Article  Google Scholar  Download

references ACKNOWLEDGEMENTS This study was financially supported by National Science Fund for Distinguished Young Scholars (No. 52025133), National Natural Science Foundation of China (No.

52261135633), China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Research, the Beijing Natural Science Foundation (No. Z220020), CNPC

Innovation Found (2021DQ02-1002), New Cornerstone Science Foundation through the XPLORER PRIZE, Young Elite Scientists Sponsorship Program by CAST (2021QNRC001), the National Natural Science

Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme (N_PolyU502/21), Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX0557), Talent introduction of

Chongqing University of Science and Technology (No. ckrc2021050, ckrc20230401), the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University (Project Code:

1-ZE2V), Shenzhen Fundamental Research Scheme-General Program (JCYJ20220531090807017), the Natural Science Foundation of Guangdong Province (2023A1515012219) and Departmental General

Research Fund (Project Code: ZVUL) from The Hong Kong Polytechnic University. B.H. also thanks the support from Research Centre for Carbon-Strategic Catalysis (RC-CSC), Research Institute

for Smart Energy (RISE), and Research Institute for Intelligent Wearable Systems (RI-IWEAR) of The Hong Kong Polytechnic University. We thank BSRF, NSRL and SSRF for the synchrotron beam

time. AUTHOR INFORMATION Author notes * Shi-Yu Lu & Meng Jin Present address: College of Metallurgy and Materials Engineering, Chongqing University of Science and Technology, Chongqing,

China * These authors contributed equally: Shi-Yu Lu, Bolong Huang. AUTHORS AND AFFILIATIONS * BIC-ESAT and School of Materials Science & Engineering, Peking University, Beijing, China

Shi-Yu Lu, Mingchuan Luo, Huawei Yang, Peng Zhou, Yuguang Chao, Kun Yin, Changshuai Shang, Fan Lv & Shaojun Guo * Department of Applied Biology and Chemical Technology, The Hong Kong

Polytechnic University, Hung Hom, Kowloon, China Bolong Huang & Mingzi Sun * Department of Chemistry, Tsinghua University, Beijing, China Meng Jin * School of Physical Sciences,

University of Chinese Academy of Sciences, Beijing, China Qinghua Zhang & Lin Gu * Key Laboratory of Luminescence Analysis and Molecular Sensing(Southwest University), Ministry of

Education, School of Materials and Energy, Southwest University, Chongqing, China Hui Liu * ENN Science and Technology Development Co.,Ltd., and State Key Laboratory of Coal-based Low-carbon

Energy, Langfang, China Junmei Wang & Yan Wang Authors * Shi-Yu Lu View author publications You can also search for this author inPubMed Google Scholar * Bolong Huang View author

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this author inPubMed Google Scholar CONTRIBUTIONS S.G. conceived the idea and designed this study. S.-Y.L. synthesized the samples, conducted characterization, electrochemical tests and

performed MEA device. B.H. and M.S. conducted the calculation study. M.J. and H.L. performed XPS tests. H.Y., Q.Z. and L.G. performed HAADF-STEM imaging. M.L., P.Z., Y.C., K.Y., C.S., J.W.,

Y.W. and F.L. provided suggestions on the manuscript. S.G., S.-Y.L. and B.H. wrote the paper. All authors discussed the results and edited the paper. CORRESPONDING AUTHOR Correspondence to

Shaojun Guo. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. PEER REVIEW PEER REVIEW INFORMATION _Nature Synthesis_ thanks Bo Zhang and the other,

anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the _Nature Synthesis_ team. ADDITIONAL

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stabilizes a high-valence Ru single site for efficient electrolysis. _Nat. Synth_ 3, 576–585 (2024). https://doi.org/10.1038/s44160-023-00444-x Download citation * Received: 20 January 2023

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