Abstract
When compared with pure water, hydrogen produced by seawater electrolysis has a better practical application potential. By replacing the oxygen evolution reaction (OER) and competitive chlorine evolution reaction (ClER) with the thermodynamically favorable anodic hydrazine oxidation reaction (HzOR) in alkaline seawater, energy-saving hydrogen production can be achieved. In this study, Fe/Co dual-doped Ni2P and MIL-FeCoNi heterostructures (FeCo-Ni2P@MIL-FeCoNi) arrays with simultaneous cation doping and hetero-engineering provide excellent bifunctional electrocatalytic performance for HzOR and hydrogen evolution reaction (HER) in alkaline seawater electrolyte. Overall hydrazine splitting (OHzS) in seawater is impressive, with a low cell voltage of only 400 mV required to reach 1000 mA cm−2 and stable operation for 1000 h to maintain above 500 mA cm−2. As a proof-of-concept, the OHzS system can save 3.03 kW h when producing 1.0 L of H2 when compared with the N2H4-free seawater system, resulting in energy-saving H2 production. Density functional theory calculations show that the combination of Co-doping and the fabrication of FeCo-Ni2P and MIL-FeCoNi heterointerfaces can result in a low water dissociation barrier, optimized hydrogen adsorption free energy toward HER, and favorable adsorbed dehydrogenation kinetics for HzOR. This processing route paves the way for a practical approach to the efficient utilization of hydrogen, which is abundant in the ocean energy field, to achieve a carbon-neutral hydrogen economy.
摘要
与电解纯水制氢相比, 海水电解制氢具有更大的实际应用价值. 在碱性海水中, 可以通过在热力学上有利的肼氧化反应(HzOR)代替析氧反应(OER)和析氯反应(ClER)来实现节能制氢. 在此, 我们制备了Co 掺杂的Fe-Ni2P/MIL-FeCoNi异质结构阵列(FeCo-Ni2P@MIL-FeCoNi). 得益于异质工程和阳离子掺杂的协同作用, FeCo-Ni2P@MIL-FeCoNi在碱性海水电解液中表现出优异的HzOR和析氢反应(HER)双功能电催化性能. 在海水系统中的整体肼分解(OHzS)仅需要400 mV的超低电压就能达到1000 mA cm−2的电流密度, 且可以在500 mA cm−2以上的电流密度稳定运行1000 h. 作为概念验证, 同样生产1.0 L的氢气, OHzS海水系统比无N2H4的整体海水分解系统(OWS)节省3.03 kW h的电力, 可实现节能制氢. DFT计算表明, Co离子掺杂和构建FeCo-Ni2P/MIL-FeCo-Ni异质界面的协同作用可以降低FeCo-Ni2P@MIL-FeCoNi的水解离能垒, 促进HER吸附氢和HzOR脱氢过程的热力学行为. 这项工作为有效利用海洋能源领域中无限丰度的氢助力实现碳中和提供了一种实用途径.
Article PDF
Similar content being viewed by others
References
Wu Y, Tao X, Qing Y, et al. Cr-doped FeNi-P nanoparticles encapsulated into N-doped carbon nanotube as a robust bifunctional catalyst for efficient overall water splitting. Adv Mater, 2019, 31: 1900178
Yan H, Xie Y, Wu A, et al. Anion-modulated HER and OER activities of 3D Ni-V-based interstitial compound heterojunctions for high-efficiency and stable overall water splitting. Adv Mater, 2019, 31: 1901174
Wu Y, Wang H, Ji S, et al. Engineered porous Ni2P-nanoparticle/Ni2P-nanosheet arrays via the Kirkendall effect and Ostwald ripening towards efficient overall water splitting. Nano Res, 2020, 13: 2098–2105
Song C, Liu Y, Wang Y, et al. Highly efficient oxygen evolution and stable water splitting by coupling NiFe LDH with metal phosphides. Sci China Mater, 2021, 64: 1662–1670
Gao WK, Yang M, Chi JQ, et al. In situ construction of surface defects of carbon-doped ternary cobalt-nickel-iron phosphide nanocubes for efficient overall water splitting. Sci China Mater, 2019, 62: 1285–1296
Jin H, Wang X, Tang C, et al. Stable and highly efficient hydrogen evolution from seawater enabled by an unsaturated nickel surface nitride. Adv Mater, 2021, 33: 2007508
Wang C, Zhu M, Cao Z, et al. Heterogeneous bimetallic sulfides based seawater electrolysis towards stable industrial-level large current density. Appl Catal B-Environ, 2021, 291: 120071
Feng W, Chen H, Zhang Q, et al. Lanthanide-regulated oxygen evolution activity of face-sharing IrO6 dimers in 6H-perovskite electrocatalysts. Chin J Catal, 2020, 41: 1692–1697
Tao L, Guo P, Zhu W, et al. Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction. Chin J Catal, 2020, 41: 1855–1863
Li X, Xue W, Mo R, et al. In situ growth of minimal Ir-incorporated CoxNi1−xO nanowire arrays on Ni foam with improved electrocatalytic activity for overall water splitting. Chin J Catal, 2019, 40: 1576–1584
Yu L, Zhu Q, Song S, et al. Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater electrolysis. Nat Commun, 2019, 10: 5106
Zang W, Sun T, Yang T, et al. Efficient hydrogen evolution of oxidized Ni-N3 defective sites for alkaline freshwater and seawater electrolysis. Adv Mater, 2021, 33: 2003846
Wu L, Yu L, Zhang F, et al. Heterogeneous bimetallic phosphide Ni2P-Fe2P as an efficient bifunctional catalyst for water/seawater splitting. Adv Funct Mater, 2021, 31: 2006484
Liu G, Sun Z, Zhang X, et al. Vapor-phase hydrothermal transformation of a nanosheet array structure Ni(OH)2 into ultrathin Ni3S2 nanosheets on nickel foam for high-efficiency overall water splitting. J Mater Chem A, 2018, 6: 19201–19209
Li Y, Zhang J, Liu Y, et al. Partially exposed RuP2 surface in hybrid structure endows its bifunctionality for hydrazine oxidation and hydrogen evolution catalysis. Sci Adv, 2020, 6: b4197
Li Y, Li J, Qian Q, et al. Superhydrophilic Ni-based multicomponent nanorod-confined-nanoflake array electrode achieves waste-battery-driven hydrogen evolution and hydrazine oxidation. Small, 2021, 17: 2008148
Luo Y, Tang L, Khan U, et al. Morphology and surface chemistry engineering toward pH-universal catalysts for hydrogen evolution at high current density. Nat Commun, 2019, 10: 269
Yu L, Wu L, McElhenny B, et al. Ultrafast room-temperature synthesis of porous S-doped Ni/Fe (oxy)hydroxide electrodes for oxygen evolution catalysis in seawater splitting. Energy Environ Sci, 2020, 13: 3439–3446
Qian Q, Li Y, Liu Y, et al. Hierarchical multi-component nanosheet array electrode with abundant NiCo/MoNi4 heterostructure interfaces enables superior bifunctionality towards hydrazine oxidation assisted energy-saving hydrogen generation. Chem Eng J, 2021, 414: 128818
Qian Q, Zhang J, Li J, et al. Artificial heterointerfaces achieve delicate reaction kinetics towards hydrogen evolution and hydrazine oxidation catalysis. Angew Chem Int Ed, 2021, 60: 5984–5993
Liu X, He J, Zhao S, et al. Self-powered H2 production with bifunctional hydrazine as sole consumable. Nat Commun, 2018, 9: 4365
Zhao M, Li H, Li W, et al. Ru-doping enhanced electrocatalysis of metal-organic framework nanosheets toward overall water splitting. Chem Eur J, 2020, 26: 17091–17096
Xie M, Ma Y, Lin D, et al. Bimetal-organic framework MIL-53(Co-Fe): An efficient and robust electrocatalyst for the oxygen evolution reaction. Nanoscale, 2020, 12: 67–71
Wu F, Guo X, Hao G, et al. Electrodeposition of sulfur-engineered amorphous nickel hydroxides on MIL-53(Fe) nanosheets to accelerate the oxygen evolution reaction. Nanoscale, 2019, 11: 14785–14792
Ren S, Duan X, Ge F, et al. Trimetal-based N-doped carbon nanotubes arrays on Ni foams as self-supported electrodes for hydrogen/oxygen evolution reactions and water splitting. J Power Sources, 2020, 480: 228866
Li FL, Shao Q, Huang X, et al. Nanoscale trimetallic metal-organic frameworks enable efficient oxygen evolution electrocatalysis. Angew Chem Int Ed, 2018, 57: 1888–1892
Salcedo-Abraira P, Vilela SMF, Babaryk AA, et al. Nickel phosphonate MOF as efficient water splitting photocatalyst. Nano Res, 2021, 14: 450–457
Sun H, Lian Y, Yang C, et al. A hierarchical nickel-carbon structure templated by metal-organic frameworks for efficient overall water splitting. Energy Environ Sci, 2018, 11: 2363–2371
Qiu B, Cai L, Wang Y, et al. Fabrication of nickel-cobalt bimetal phosphide nanocages for enhanced oxygen evolution catalysis. Adv Funct Mater, 2018, 28: 1706008
Chen D, Lu R, Pu Z, et al. Ru-doped 3D flower-like bimetallic phosphide with a climbing effect on overall water splitting. Appl Catal B-Environ, 2020, 279: 119396
Zhang H, Zhou W, Dong J, et al. Intramolecular electronic coupling in porous iron cobalt (oxy)phosphide nanoboxes enhances the electro-catalytic activity for oxygen evolution. Energy Environ Sci, 2019, 12: 3348–3355
Wang Z, Yang J, Wang W, et al. Hollow cobalt-nickel phosphide nanocages for efficient electrochemical overall water splitting. Sci China Mater, 2021, 64: 861–869
Zhang SL, Guan BY, Lou XWD. Co-Fe alloy/N-doped carbon hollow spheres derived from dual metal-organic frameworks for enhanced electrocatalytic oxygen reduction. Small, 2019, 15: 1805324
Yu X, Zhao J, Johnsson M. Interfacial engineering of nickel hydroxide on cobalt phosphide for alkaline water electrocatalysis. Adv Funct Mater, 2021, 31: 2101578
Lin Y, Wang H, Peng CK, et al. Co-induced electronic optimization of hierarchical NiFe LDH for oxygen evolution. Small, 2020, 16: 2002426
Sun F, Wang G, Ding Y, et al. NiFe-based metal-organic framework nanosheets directly supported on nickel foam acting as robust electrodes for electrochemical oxygen evolution reaction. Adv Energy Mater, 2018, 8: 1800584
Acknowledgements
This work was supported by the National Natural Science Foundation of China (51772162 and 52072197), China Postdoctoral Science Foundation (2020M682135), the Postdoctoral Applied Research Project of Qingdao, the Outstanding Youth Foundation of Shandong Province, China (ZR2019JQ14), the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions (2019KJC004), the Major Scientific and Technological Innovation Project (2019JZZY020405), the Major Basic Research Program of Natural Science Foundation of Shandong Province (ZR2020ZD09), and Taishan Scholar Young Talent Program (tsqn201909114).
Author information
Authors and Affiliations
Contributions
Author contributions Liu X designed and engineered the samples; Yu Q and Chi J performed the experiments; Yu Q wrote the paper with support from Wang L; Chi J helped to modify the manuscript; all authors contributed to the general discussion.
Corresponding authors
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Supplementary information Experimental details and supporting data are available in the online version of the paper.
Qingping Yu is currently a master’s candidate at Qingdao University of Science and Technology. She received her BSc degree from Qingdao University of Science and Technology (2020). Her research interests focus on the design and synthesis of MOF-derived materials for sea-water splitting.
Jingqi Chi received a BSc degree from China University of Petroleum (East China). She received her MSc degree and PhD degree from the State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China). She is currently an associate professor at Qingdao University of Science and Technology. Her research interests focus on the design and synthesis of transition metal-based nanostructures and porous MOFs materials for electrochemical applications.
Xiaobin Liu is currently a postdoctor at Qingdao University of Science and Technology. He received his PhD degree from the Institute for Advanced Materials and Technology, University of Science and Technology Beijing. His research interests focus on the synthesis and application of MOF-derived materials.
Lei Wang obtained his PhD degree in chemistry from Jilin University in 2006 under the supervision of Prof. Shouhua Feng. He moved to the State Key Laboratory of Crystal Materials, Shandong University, as a postdoctoral scholar from 2008 to 2010. He is currently a professor of chemistry at Qingdao University of Science and Technology. His research interests mainly focus on the design and synthesis of functional organic-inorganic hybrids and porous MOFs materials, as well as their applications in photocatalysis, electrocatalysis, lithium-ion battery, etc.
Supporting Information
40843_2021_1928_MOESM1_ESM.pdf
Dual-strategy of hetero-engineering and cation doping to boost energy-saving hydrogen production via hydrazine-assisted seawater electrolysis
Supplementary material, approximately 8.62 MB.
Supplementary material, approximately 6.84 MB.
Supplementary material, approximately 1.57 MB.
Rights and permissions
About this article
Cite this article
Yu, Q., Chi, J., Liu, G. et al. Dual-strategy of hetero-engineering and cation doping to boost energy-saving hydrogen production via hydrazine-assisted seawater electrolysis. Sci. China Mater. 65, 1539–1549 (2022). https://doi.org/10.1007/s40843-021-1928-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-021-1928-7