Modulating the Local Charge Distribution of Single-Atomic Ru Sites for an Efficient Hydrogen Evolution Reaction

Abstract

Ruthenium (Ru)-based electrocatalysts show great promise as substitutes for platinum (Pt) for the alkaline hydrogen evolution reaction (HER) because of their efficient water dissociation capabilities. Nevertheless, the strong adsorption of Ru–OH intermediates (Ru-OH_ad) blocks the active site, leading to unsatisfactory HER performance. In this study, we report a universal ligand-exchange strategy for synthesizing a MOF-on-MOF-derived FeP–CoP heterostructure-anchored Ru single-atom site catalyst (Ru-FeP-CoP/NPC). The obtained catalyst shows a low overpotential (28 mV at 10 mA cm⁻²) and a high mass activity (9.29 A mg⁻¹ at 100 mV), surpassing the performance of commercial Pt/C by a factor of 46. Theoretical studies show that regulating the local charge distribution of Ru single-atom sites could alleviate surrounding OH⁻ blockages, accelerating water dissociation and facilitating hydrogen adsorption/desorption, thus enhancing HER activity. This work aims to inspire further design of highly active and durable electrocatalysts with tailored electronic properties for high-purity hydrogen production.

Keywords

heterostructure catalyst / hydrogen evolution reaction / ligand exchange / metal–organic frameworks

References

[1] Z. Y. Yu, Y. Duan, X. Y. Feng, X. Yu, M. R. Gao, and S. H. Yu, “Clean and Affordable Hydrogen Fuel From Alkaline Water Splitting: Past, Recent Progress, and Future Prospects,” Advanced Materials 33, no. 31 (2021): 2007100.

[2] S. Jiang, R. Zhang, H. Liu, et al., “Promoting Formation of Oxygen Vacancies in Two-Dimensional Cobalt-Doped Ceria Nanosheets for Efficient Hydrogen Evolution,” Journal of the American Chemical Society 142, no. 14 (2020): 6461-6466.

[3] B. Liu, X. Lan, Q. Zhong, and T. Wang, “Metal Phosphide: An Atypical Catalytic Site,” ACS Catalysis 14, no. 2 (2024): 757-775.

[4] F. Nie, Z. Yang, X. Dai, et al., “Synergistic Coupling of Heterostructured Porous CoP Nanosheets With P Doped NiO for Highly Efficient Overall Alkaline Water Splitting,” Journal of Colloid and Interface Science 621 (2022): 213-221.

[5] B. Zhang, Y. Zheng, T. Ma, et al., “Designing MOF Nanoarchitectures for Electrochemical Water Splitting,” Advanced Materials 33, no. 17 (2021): 2006042.

[6] M. Rinawati, Y.-X. Wang, K.-Y. Chen, and M.-H. Yeh, “Designing a Spontaneously Deriving NiFe-LDH From Bimetallic MOF-74 as an Electrocatalyst for Oxygen Evolution Reaction in Alkaline Solution,” Chemical Engineering Journal 423 (2021): 130204.

[7] W. Song, M. Li, C. Wang, and X. Lu, “Electronic Modulation and Interface Engineering of Electrospun Nanomaterials-Based Electrocatalysts Toward Water Splitting,” Carbon Energy 3, no. 1 (2020): 101-128.

[8] Q. Zhou, R. Sun, Y. Ren, et al., “Reactive Template-Derived Interfacial Engineering of CoP/CoO Heterostructured Porous Nanotubes Towards Superior Electrocatalytic Hydrogen Evolution,” Carbon Energy 5, no. 1 (2023): e273.

[9] J. Li, Y. Tan, M. Zhang, et al., “Boosting Electrocatalytic Activity of Ru for Acidic Hydrogen Evolution Through Hydrogen Spillover Strategy,” ACS Energy Letters 7, no. 4 (2022): 1330-1337.

[10] Y. Zheng, P. Shang, F. Pei, et al., “Achieving an Efficient Hydrogen Evolution Reaction With a Bicontinuous Nanoporous Ptnimg Alloy of Ultralow Noble-Metal Content at an Ultrawide Range of Current Densities,” Chemical Engineering Journal 433 (2022): 134571.

[11] D. Li, C. Zhou, R. Yang, et al., “Interfacial Engineering of the Co_xP-Fe₂P Heterostructure for Efficient and Robust Electrochemical Overall Water Splitting,” ACS Sustainable Chemistry & Engineering 9, no. 23 (2021): 7737-7748.

[12] A. Li, L. Zhang, F. Wang, et al., “Rational Design of Porous Ni-Co-Fe Ternary Metal Phosphides Nanobricks as Bifunctional Electrocatalysts for Efficient Overall Water Splitting,” Applied Catalysis B: Environmental 310 (2022): 121353.

[13] M. Wang, X. Liu, and X. Wu, “Realizing Efficient Electrochemical Overall Water Electrolysis Through Hierarchical CoP@NiCo-LDH Nanohybrids,” Nano Energy 114 (2023): 108681.

[14] J.-Z. Zhang, Z. Zhang, H.-B. Zhang, et al., “Prussian-Blue-Analogue-Derived Ultrathin Co₂P-Fe₂P Nanosheets for Universal-pH Overall Water Splitting,” Nano Letters 23, no. 17 (2023): 8331-8338.

[15] M. Afshan, P. K. Sachdeva, D. Rani, et al., “Porous Carbon Template Decorated With MOF- Driven Bimetallic Phosphide: A Suitable Heterostructure for the Production of Uninterrup-Ted Green Hydrogen via Renewable Energy Storage Device,” Small 19, no. 50 (2023): 2304399.

[16] Q. Wang and D. Astruc, “State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis,” Chemical Reviews 120, no. 2 (2020): 1438-1511.

[17] X. Xu, H.-C. Chen, L. Li, et al., “Leveraging Metal Nodes in Metal-Organic Frameworks for Advanced Anodic Hydrazine Oxidation Assisted Seawater Splitting,” ACS Nano 17, no. 11 (2023): 10906-10917.

[18] Z. Qiu, Y. Li, Y. Gao, et al., “2D MOF-Assisted Pyrolysis-Displacement-Alloying Synthesis of High-Entropy Alloy Nanoparticles Library for Efficient Electrocatalytic Hydrogen Oxidation,” Angewandte Chemie International Edition 62, no. 33 (2023): e202306881.

[19] G. Zhang, Y. Li, X. Xiao, et al., “In Situ Anchoring Polymetallic Phosphide Nanoparticles Within Porous Prussian Blue Analogue Nanocages for Boosting Oxygen Evolution Catalysis,” Nano Letters 21, no. 7 (2021): 3016-3025.

[20] F. Zhang, X. Wang, W. Han, et al., “The Synergistic Activation of Ce-Doping and CoP/Ni₃P Hybrid Interaction for Efficient Water Splitting at Large-Current-Density,” Advanced Functional Materials 33, no. 9 (2023): 2212381.

[21] J. Zou, S. Wu, Y. Lin, et al., “Electronic Phosphide-Support Interactions in Carbon-Supported Molybdenum Phosphide Catalysts Derived From Metal-Organic Frameworks,” Nano Letters 23, no. 23 (2023): 10955-10963.

[22] B. Liu, B. Zhong, F. Li, et al., “Co₂P/CoP Heterostructures With Significantly Enhanced Performance in Electrocatalytic Hydrogen Evolution Reaction: Synthesis and Electron Redistribution Mechanism,” Nano Research 16, no. 11 (2023): 12830-12839.

[23] W. Yu, Q. Li, W. Xiao, et al., “Unique CoP Microflower Decorated With Phosphorous Enriched PtP₂ Onto Nickel Foam With Interfacial Electronic Interactions to Boost Alkali Water-Splitting,” Adv Funct Mater 34, no. 27 (2024): 2313935.

[24] Y. Zhao, H. Zhang, J. Chen, et al., “Interfacial Electronic Engineering of Heterostructured Co₂P-Monip/NF Nano-Sea-Urchin Catalysts for Efficient and Stable Hydrogen Evolution via Water/Seawater Splitting,” Chemical Engineering Journal 477 (2023): 147092.

[25] W. Yu, Y. Gao, Z. Chen, Y. Zhao, Z. Wu, and L. Wang, “Strategies on Improving the Electrocata-Lytic Hydrogen Evolution Performances of Metal Phosphides,” Chinese Journal of Catalysis 42, no. 11 (2021): 1876-1902.

[26] T. Bligaard, J. K. Nørskov, S. Dahl, J. Matthiesen, C. H. Christensen, and J. Sehested, “The Brønste-D-Evans-Polanyi Relation and the Volcano Curve in Heterogeneous Catalysis,” Journal of Catalysis 224, no. 1 (2004): 206-217.

[27] T. T. Yang and W. A. Saidi, “The Bell-Evans-Polanyi Relation for Hydrogen Evolution Reaction From First-Principles,” npj Computational Materials 10, no. 1 (2024): 98.

[28] X. Zheng, J. Yang, P. Li, et al., “Ir-Sn Pair-Site Triggers Key Oxygen Radical Intermediate for Efficient Acidic Water Oxidation,” Science Advances 9, no. 42 (2023): eadi8025.

[29] D. Sun, P. Qiang, Y. Yu, et al., “Electronic Modulation With Ru Nanoclusters Decorated CoP Nanowire Arrays for Alkaline and Acidic Hydrogen Evolution Reaction,” International Journal of Hydrogen Energy 59 (2024): 1205-1213.

[30] H. Sun, C.-W. Tung, Y. Qiu, et al., “Atomic Metal-Support Interaction Enables Reconstructi-On-Free Dual-Site Electrocatalyst,” Journal of the American Chemical Society 144, no. 3 (2021): 1174-1186.

[31] N. Popov, M. Bošković, M. Perović, et al., “Effect of Ru³⁺ Ions on the Formation, Structural, Magnetic and Optical Properties of Hematite (Α-Fe₂O₃) Nanorods,” Journal of Magnetism and Magnetic Materials 538 (2021): 168316.

[32] Q. Yu, W. Yu, Y. Wang, et al., “Hydroxyapatite-Derived Heterogeneous Ru-Ru₂P Electrocatalyst and Environmentally-Friendly Membrane Electrode Toward Efficient Alkaline El-Ectrolyzer,” Small 19, no. 25 (2023): 2208045.

[33] G. Zhou, G. Liu, X. Liu, et al., “1D/3D Heterogeneous Assembling Body as Trifunctional Electrocatalysts Enabling Zinc-Air Battery and Self-Powered Overall Water Splitting,” Advanced Functional Materials 32, no. 4 (2022): 2107608.

[34] M. Kumar, B. Ramulu, and J. S. Yu, “Nanoarchitectonic Ni-Doped Edge Dislocation Defect-Rich MoS₂ Boosting Catalytic Activity in Electrochemical Hydrogen Production,” Journal of Cleaner Production 414 (2023): 137589.

[35] H. Song, M. Wu, Z. Tang, J. S. Tse, B. Yang, and S. Lu, “Single Atom Ruthenium-Doped CoP/CDs Nanosheets via Splicing of Carbon-Dots for Robust Hydrogen Production,” Angewandte Chemie International Edition 60, no. 13 (2021): 7234-7244.

[36] Y. Li, Y. Wu, H. Hao, et al., “In Situ Unraveling Surface Reconstruction of Ni₅P₄@FeP Nanosheet Array for Superior Alkaline Oxygen Evolution Reaction,” Applied Catalysis B: Environmental 305 (2022): 121033.

[37] Q. Li, D. Shen, C. Luo, et al., “Ultra-Thermostability of Spatially Confined and Fully Protected Perovskite Nanocrystals by In Situ Crystallization,” Small 18, no. 15 (2022): 2107452.

[38] J. Li, Y. Hu, X. Huang, Y. Zhu, and D. Wang, “Bimetallic Phosphide Heterostructure Coupled With Ultrathin Carbon Layer Boosting Overall Alkaline Water and Seawater Splitting,” Small 19, no. 20 (2023): 2206533.

[39] X. Liang, B. Zheng, L. Chen, J. Zhang, Z. Zhuang, and B. Chen, “MOF-Derived Formation of Ni₂P-CoP Bimetallic Phosphides With Strong Interfacial Effect Toward Electrocatalytic Water Splitting,” ACS Applied Materials & Interfaces 9, no. 27 (2017): 23222-23229.

[40] Y. Wu, X. Chen, L. Su, Q. Wang, and S. Ren, “Three-Dimensional Self-Supporting Ni₂P-Ni₁₂P₅/NF Heterostructure as an Efficient Electrocatalyst to Enhance Hydrogen Evolution Reaction,” Ionics 28 (2022): 3935-3944.

[41] Y. Zhang, R. Lu, C. Wang, Y. Zhao, and L. Qi, “Electronic and Vacancy Engineering of Mo-Ru-CoO_x Nanoarrays for High-Efficiency Water Splitting,” Adv Funct Mater 33, no. 40 (2023): 2303073.

[42] G. Meng, Y. Chen, R. Wang, et al., “Co-W Bimetallic Carbide Nanocatalysts: Computational Exploration, Confined Disassembly-Assembly Synthesis and Alkaline/Seawater Hydrogen Evolution,” Small 18, no. 48 (2022): 2204443.

[43] P. Zhou, L. Wang, J. Lv, et al., “Tuning the Electronic Structure of Co@N-C Hybrids via Metal-Doping for Efficient Electrocatalytic Hydrogen Evolution Reaction,” Journal of Materials Chemistry A 10, no. 9 (2022): 4981-4991.

[44] Z. Wang, H. Liu, R. Ge, et al., “Phosphorus-Doped Co₃O₄ Nanowire Array: A Highly Efficient Bifunctional Electrocatalyst for Overall Water Splitting,” ACS Catalysis 8, no. 3 (2018): 2236-2241.

[45] X. Li, T. Wu, N. Li, et al., “Vertically Staggered Porous Ni₂P/Fe₂P Nanosheets With Trace Ru Doping as Bifunctional Electrocatalyst for Alkaline Seawater Splitting,” Advanced Functional Materials 34, no. 23 (2024): 2400734.

[46] X. Wang, H. Yao, C. Zhang, et al., “Double-Tuned RuCo Dual Metal Single Atoms and Nanoalloy With Synchronously Expedited Volmer/Tafel Kinetics for Effective and Ultrastable Ampere-Level Current Density Hydrogen Production,” Advanced Functional Materials 33, no. 40 (2023): 2301804.

[47] H. Shang, Z. Zhao, J. Pei, et al., “Dynamic Evolution of Isolated Ru-FeP Atomic Interface Sites for Promoting the Electrochemical Hydrogen Evolution Reaction,” Journal of Materials Chemistry A 8, no. 43 (2020): 22607-22612.

[48] L. Wang, M. Ma, C. Zhang, et al., “Manipulating the Microenvironment of Single Atoms by Switching Support Crystallinity for Industrial Hydrogen Evolution,” Angewandte Chemie 136, no. 7 (2024): e202317220.

[49] P. Wang, K. Wang, Y. Liu, et al., “Dual-Type Ru Atomic Sites for Efficient Alkaline Overall Water Splitting,” Advanced Functional Materials 34, no. 36 (2024): 2316709.

[50] W. Chen, M. Yu, S. Liu, C. Zhang, S. Jiang, and G. Duan, “Recent Progress of Ru Single-Atom Catalyst: Synthesis, Modification, and Energetic Applications,” Advanced Functional Materials 34, no. 22 (2024): 2313307.

[51] X. Lin, W. Hu, J. Xu, et al., “Alleviating OH Blockage on the Catalyst Surface by the Puncture Effect of Single-Atom Sites to Boost Alkaline Water Electrolysis,” Journal of the American Chemical Society 146, no. 7 (2024): 4883-4891.

[52] Q. Dai, L. Wang, K. Wang, et al., “Accelerated Water Dissociation Kinetics by Electron-Enriched Cobalt Sites for Efficient Alkaline Hydrogen Evolution,” Advanced Functional Materials 32, no. 12 (2022): 2109556.

[53] Y. Zheng, Y. Jiao, M. Jaroniec, and S. Z. Qiao, “Advancing the Electrochemistry of the Hydrogen-Evolution Reaction Through Combining Experiment and Theory,” Angewandte Chemie International Edition 54, no. 1 (2015): 52-65.

[54] H. Zhang, A. Aierke, Y. Zhou, et al., “A High-Performance Transition-Metal Phosphide Electrocatalyst for Converting Solar Energy Into Hydrogen at 19.6% STH Efficiency,” Carbon Energy 5, no. 1 (2023): 1-12.

[55] J. Chen, Y. Zhao, S. Zhou, et al., “Heterogeneous Bimetallic Oxides/Phosphides Nanorod With Upshifted d Band Center for Efficient Overall Water Splitting,” Chinese Chemical Letters 35, no. 9 (2024): 109268.

[56] L. Yang, Z. Ni, Y. Zhao, et al., “Interfacial Electric Field Stabilized Ru Single-Atom Catalysts for Efficient Water Oxidation,” ACS Catalysis 14, no. 14 (2024): 10820-10828.

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