Abstract
Bifunctional catalysts for hydrogen/oxygen evolution reactions (HER/OER) are urgently needed given the bright future of water splitting hydrogen production technology. Here, the self-supporting N and Ce dual-doped NiCoP nanoarrays (denoted N,Ce-NiCoP/NF) grown on Ni foam are successfully constructed. When the N,Ce-NiCoP/NF simultaneously acts as the HER and OER electrodes, the voltages of 1.54 and 2.14 V are obtained for driving 10 and 500 mA·cm−2 with a robust durability, and demonstrate its significant potential for practical water electrolysis. According to both experiments and calculations, the electronic structure of NiCoP may be significantly altered by strategically incorporating N and Ce into the lattice, which in turn optimizes the Gibbs free energy of HER/OER intermediates and speeds up the water splitting kinetics. Moreover, the sprout-shaped morphology significantly increases the exposure of active sites and facilitates charge/mass transfer, thereby augmenting catalyst performance. This study offers a potentially effective approach involving the regulation of anion and cation double doping, as well as architectural engineering, for the purpose of designing and optimizing innovative electrocatalysts.
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Riyajuddin, S.; Azmi, K.; Pahuja, M.; Kumar, S.; Maruyama, T.; Bera, C.; Ghosh, K. Super-hydrophilic hierarchical Ni-foam-graphene-carbon nanotubes-Ni2P-CuP2 nano-architecture as efficient electrocatalyst for overall water splitting. ACS Nano 2021, 15, 5586–5599.
Shifa, T. A.; Yusupov, K.; Solomon, G.; Gradone, A.; Mazzaro, R.; Cattaruzza, E.; Vomiero, A. In situ-generated oxide in Sn-doped nickel phosphide enables ultrafast oxygen evolution. ACS Catal. 2021, 11, 4520–4529.
Wang, D. W.; Li, Q.; Han, C.; Lu, Q. Q.; Xing, Z. C.; Yang, X. R. Atomic and electronic modulation of self-supported nickel-vanadium layered double hydroxide to accelerate water splitting kinetics. Nat. Commun. 2019, 10, 3899.
Wang, H. M.; Chen, Z. N.; Wu, D. S.; Cao, M. N.; Sun, F. F.; Zhang, H.; You, H. H.; Zhuang, W.; Cao, R. Significantly enhanced overall water splitting performance by partial oxidation of Ir through Au modification in core–shell alloy structure. J. Am. Chem. Soc. 2021, 143, 4639–4645.
Zhai, P. L.; Xia, M. Y.; Wu, Y. Z.; Zhang, G. H.; Gao, J. F.; Zhang, B.; Cao, S. Y.; Zhang, Y. T.; Li, Z. W.; Fan, Z. Z. et al. Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting. Nat. Commun. 2021, 12, 4587.
Zhang, H. J.; Maijenburg, A. W.; Li, X. P.; Schweizer, S. L.; Wehrspohn, R. B. Bifunctional heterostructured transition metal phosphides for efficient electrochemical water splitting. Adv. Funct. Mater. 2020, 30, 2003261.
Suryawanshi, U. P.; Ghorpade, U. V.; Lee, D. M.; He, M. R.; Shin, S. W.; Kumar, P. V.; Jang, J. S.; Jung, H. R.; Suryawanshi, M. P.; Kim, J. H. Colloidal Ni2P nanocrystals encapsulated in heteroatom-doped graphene nanosheets: A synergy of 0D@2D heterostructure toward overall water splitting. Chem. Mater. 2021, 33, 234–245.
Lv, X. D.; Li, X. T.; Yang, C.; Ding, X. Q.; Zhang, Y. F.; Zheng, Y. Z.; Li, S. Q.; Sun, X. N.; Tao, X. Large-size, porous, ultrathin NiCoP nanosheets for efficient electro/photocatalytic water splitting. Adv. Funct. Mater. 2020, 30, 1910830.
Chen, L.; Song, Y. H.; Liu, Y.; Xu, L.; Qin, J. Q.; Lei, Y. P.; Tang, Y. G. NiCoP nanoleaves array for electrocatalytic alkaline H2 evolution and overall water splitting. J. Energy Chem. 2020, 50, 395–401.
Tang, W. G.; Zhu, S. L.; Jiang, H.; Liang, Y. Q.; Li, Z. Y.; Wu, S. L.; Cui, Z. D. Self-supporting nanoporous CoMoP electrocatalyst for hydrogen evolution reaction in alkaline solution. J. Colloid Interface Sci. 2022, 625, 606–613.
Kang, Q. L.; Li, M. Y.; Shi, J. W.; Lu, Q. Y.; Gao, F. A universal strategy for carbon-supported transition metal phosphides as highperformance bifunctional electrocatalysts towards efficient overall water splitting. ACS Appl. Mater. Interfaces 2020, 12, 19447–19456.
El-Refaei, S. M.; Russo, P. A.; Pinna, N. Recent advances in multimetal and doped transition-metal phosphides for the hydrogen evolution reaction at different pH values. ACS Appl. Mater. Interfaces 2021, 13, 22077–22097.
Jiao, S. L.; Fu, X. W.; Wang, S. Y.; Zhao, Y. Perfecting electrocatalysts via imperfections: Towards the large-scale deployment of water electrolysis technology. Energy Environ. Sci. 2021, 14, 1722–1770.
Song, H. R.; Wang, J. S.; Zhang, Z. F.; Shai, X.; Guo, Y. Z. Synergistic balancing hydrogen and hydroxyl adsorption/desorption of nickel sulfide via cation and anion dual-doping for boosting alkaline hydrogen evolution. Chem. Eng. J. 2021, 420, 129842.
Thiyagarajan, D.; Gao, M. Y.; Sun, L.; Dong, X. C.; Zheng, D. H.; Abdul Wahab, M.; Will, G.; Lin, J. J. Nanoarchitectured porous Cu-CoP nanoplates as electrocatalysts for efficient oxygen evolution reaction. Chem. Eng. J. 2022, 432, 134303.
Sun, H.; Min, Y. X.; Yang, W. J.; Lian, Y. B.; Lin, L.; Feng, K.; Deng, Z.; Chen, M. Z.; Zhong, J.; Xu, L. et al. Morphological and electronic tuning of Ni2P through iron doping toward highly efficient water splitting. ACS Catal. 2019, 9, 8882–8892.
Liu, Y. H.; Ran, N.; Ge, R. Y.; Liu, J. J.; Li, W. X.; Chen, Y. Y.; Feng, L. Y.; Che, R. C. Porous Mn-doped cobalt phosphide nanosheets as highly active electrocatalysts for oxygen evolution reaction. Chem. Eng. J. 2021, 425, 131642.
Liu, J. Y.; Liu, Y.; Mu, X. L.; Jang, H.; Lei, Z. W.; Jiao, S. H.; Yan, P. F.; Kim, M. G.; Cao, R. G. Boosting activity and stability of electrodeposited amorphous Ce-doped NiFe-based catalyst for electrochemical water oxidation. Adv. Funct. Mater. 2022, 32, 2204086.
Wu, X. X.; Zhang, T.; Wei, J. X.; Feng, P. F.; Yan, X. B.; Tang, Y. Facile synthesis of Co and Ce dual-doped Ni3S2 nanosheets on Ni foam for enhanced oxygen evolution reaction. Nano Res. 2020, 13, 2130–2135.
Zhong, H. H.; Alberto Estudillo-Wong, L.; Gao, Y.; Feng, Y. J.; Alonso-Vante, N. Oxygen vacancies engineering by coordinating oxygen-buffering CeO2 with CoO nanorods as efficient bifunctional oxygen electrode electrocatalyst. J. Energy Chem. 2021, 59, 615–625.
Wu, Q.; Gao, Q. P.; Sun, L. M.; Guo, H. M.; Tai, X. S.; Li, D.; Liu, L.; Ling, C. Y.; Sun, X. P. Facilitating active species by decorating CeO2 on Ni3S2 nanosheets for efficient water oxidation electrocatalysis. Chinese J. Catal. 2021, 42, 482–489.
Zai, S. F.; Gao, X. Y.; Yang, C. C.; Jiang, Q. Ce-modified Ni(OH)2 nanoflowers supported on NiSe2 octahedra nanoparticles as high-efficient oxygen evolution electrocatalyst. Adv. Energy Mater. 2021, 11, 2101266.
Xu, H. J.; Shan, C. F.; Wu, X. X.; Sun, M. Z.; Huang, B. L.; Tang, Y.; Yan, C. H. Fabrication of layered double hydroxide microcapsules mediated by cerium doping in metal-organic frameworks for boosting water splitting. Energy Environ. Sci. 2020, 13, 2949–2956.
Zhang, R.; Huang, J.; Chen, G. L.; Chen, W.; Song, C. S.; Li, C. R.; Ostrikov, K. In situ engineering bi-metallic phospho-nitride bifunctional electrocatalysts for overall water splitting. Appl. Catal. B: Environ. 2019, 254, 414–423.
Zhou, G. Y.; Ma, Y. R.; Wu, X. M.; Lin, Y. Z.; Pang, H.; Zhang, M. Y.; Xu, L.; Tian, Z. Q.; Tang, Y. W. Electronic modulation by N incorporation boosts the electrocatalytic performance of urchin-like Ni5P4 hollow microspheres for hydrogen evolution. Chem. Eng. J. 2020, 402, 126302.
Chang, J. F.; Wang, G. Z.; Yang, Z. Z.; Li, B. Y.; Wang, Q.; Kuliiev, R.; Orlovskaya, N.; Gu, M.; Du, Y. G.; Wang, G. F. et al. Dualdoping and synergism toward high-performance seawater electrolysis. Adv. Mater. 2021, 33, 2101425.
Kim, D.; Qin, X. Y.; Yan, B. Y.; Piao, Y. Sprout-shaped Mo-doped CoP with maximized hydrophilicity and gas bubble release for high-performance water splitting catalyst. Chem. Eng. J. 2021, 408, 127331.
He, L.; Gong, L.; Gao, M.; Yang, C. W.; Sheng, G. P. In situ formation of NiCoP@phosphate nanocages as an efficient bifunctional electrocatalyst for overall water splitting. Electrochim. Acta 2020, 337, 135799.
Liu, H.; Ma, X.; Hu, H.; Pan, Y. Y.; Zhao, W. N.; Liu, J. L.; Zhao, X. Y.; Wang, J. L.; Yang, Z. X.; Zhao, Q. S. et al. Robust NiCoP/CoP heterostructures for highly efficient hydrogen evolution electrocatalysis in alkaline solution. ACS Appl. Mater. Interfaces 2019, 11, 15528–15536.
Boppella, R.; Tan, J.; Yang, W.; Moon, J. Homologous CoP/NiCoP heterostructure on N-doped carbon for highly efficient and pH-universal hydrogen evolution electrocatalysis. Adv. Funct. Mater. 2019, 29, 1807976.
Hu, E. L.; Ning, J. Q.; Zhao, D.; Xu, C. Y.; Lin, Y. Y.; Zhong, Y. J.; Zhang, Z. Y.; Wang, Y. J.; Hu, Y. A room-temperature postsynthetic ligand exchange strategy to construct mesoporous Fe-doped CoP hollow triangle plate arrays for efficient electrocatalytic water splitting. Small 2018, 14, 1704233.
Xu, X. J.; Du, P. Y.; Guo, T.; Zhao, B. L.; Wang, H. L.; Huang, M. H. In situ grown Ni phosphate@Ni12P5 nanorod arrays as a unique core–shell architecture: Competitive bifunctional electrocatalysts for urea electrolysis at large current densities. ACS Sustainable Chem. Eng. 2020, 8, 7463–7471.
Wang, C.; Zhang, L.; Xu, G. C.; Yang, L. F.; Yang, J. H. Construction of unique ternary composite MCNTs@CoSx@MoS2 with three-dimensional lamellar heterostructure as high-performance bifunctional electrocatalysts for hydrogen evolution and oxygen evolution reactions. Chem. Eng. J. 2021, 417, 129270.
Wang, Y. F.; Chen, Z.; Han, P.; Du, Y. H.; Gu, Z. X.; Xu, X.; Zheng, G. F. Single-atomic Cu with multiple oxygen vacancies on ceria for electrocatalytic CO2 reduction to CH4. ACS Catal. 2018, 8, 7113–7119.
Liu, S. J.; Zhu, J.; Sun, M.; Ma, Z. X.; Hu, K.; Nakajima, T.; Liu, X. H.; Schmuki, P.; Wang, L. Promoting the hydrogen evolution reaction through oxygen vacancies and phase transformation engineering on layered double hydroxide nanosheets. J. Mater. Chem. A 2020, 8, 2490–2497.
Shao, Z. Y.; Qi, H.; Wang, X.; Sun, J.; Guo, N. K.; Huang, K. K.; Wang, Q. Boosting oxygen evolution by surface nitrogen doping and oxygen vacancies in hierarchical NiCo/NiCoP hybrid nanocomposite. Electrochim. Acta 2019, 296, 259–267.
Xu, T. Y.; Jiao, D. X.; Zhang, L.; Zhang, H. Y.; Zheng, L. R.; Singh, D. J.; Zhao, J. X.; Zheng, W. T.; Cui, X. Q. Br-induced P-poor defective nickel phosphide for highly efficient overall water splitting. Appl. Catal. B: Environ. 2022, 316, 121686.
Lin, Y.; Sun, K. A.; Liu, S. J.; Chen, X. M.; Cheng, Y. S.; Cheong, W. C.; Chen, Z.; Zheng, L. R.; Zhang, J.; Li, X. Y. et al. Construction of CoP/NiCoP nanotadpoles heterojunction interface for wide pH hydrogen evolution electrocatalysis and supercapacitor. Adv. Energy Mater. 2019, 9, 1901213.
Liu, Y.; Feng, Q. G.; Liu, W.; Li, Q.; Wang, Y. C.; Liu, B.; Zheng, L. R.; Wang, W.; Huang, L.; Chen, L. M. et al. Boosting interfacial charge transfer for alkaline hydrogen evolution via rational interior Se modification. Nano Energy 2021, 81, 105641.
Chen, L.; Wang, Y. P.; Zhao, X.; Wang, Y. C.; Li, Q.; Wang, Q. C.; Tang, Y. G.; Lei, Y. P. Trimetallic oxyhydroxides as active sites for large-current-density alkaline oxygen evolution and overall water splitting. J. Mater. Sci. Technol. 2022, 110, 128–135.
Zhang, Y.; Guo, H. R.; Li, X. P.; Du, J.; Ren, W. L.; Song, R. A 3D multi-interface structure of coral-like Fe-Mo-S/Ni3S2@NF using for high-efficiency and stable overall water splitting. Chem. Eng. J. 2021, 404, 126483.
Li, X. Y.; Xiao, L. P.; Zhou, L.; Xu, Q. C.; Weng, J.; Xu, J.; Liu, B. Adaptive bifunctional electrocatalyst of amorphous CoFe oxide@2D black phosphorus for overall water splitting. Angew. Chem., Int. Ed. 2020, 59, 21106–21113.
Jin, R. X.; Huang, J.; Chen, G. L.; Chen, W.; Ouyang, B.; Chen, D. L.; Kan, E. J.; Zhu, H.; Li, C. R.; Yang, D. Z. et al. Water-sprouted, plasma-enhanced Ni-Co phospho-nitride nanosheets boost electrocatalytic hydrogen and oxygen evolution. Chem. Eng. J. 2020, 402, 126257.
Liu, W. X.; Yu, L. H.; Yin, R. L.; Xu, X. L.; Feng, J. X.; Jiang, X.; Zheng, D.; Gao, X. L.; Gao, X. B.; Que, W. B. et al. Non-3d metal modulation of a 2D Ni-Co heterostructure array as multifunctional electrocatalyst for portable overall water splitting. Small 2020, 16, 1906775.
Wang, P. Y.; Zhang, L.; Wang, Z.; Bu, D. C.; Zhan, K.; Yan, Y.; Yang, J. H.; Zhao, B. N and Mn dual-doped cactus-like cobalt oxide nanoarchitecture derived from cobalt carbonate hydroxide as efficient electrocatalysts for oxygen evolution reactions. J. Colloid Interface Sci. 2021, 597, 361–369.
Yao, N.; Li, P.; Zhou, Z. R.; Meng, R.; Cheng, G. Z.; Luo, W. Nitrogen engineering on 3D dandelion-flower-like CoS2 for highperformance overall water splitting. Small 2019, 15, 1901993.
He, J. T.; Liu, F.; Chen, Y. K.; Liu, X. Y.; Zhang, X. L.; Zhao, L. L.; Chang, B.; Wang, J. G.; Liu, H.; Zhou, W. J. Cathode electrochemically reconstructed V-doped CoO nanosheets for enhanced alkaline hydrogen evolution reaction. Chem. Eng. J. 2022, 432, 134331.
Wang, J.; Hu, J.; Liang, C.; Chang, L. M.; Du, Y. C.; Han, X. J.; Sun, J. M.; Xu, P. Surface reconstruction of phosphorus-doped cobalt molybdate microarrays in electrochemical water splitting. Chem. Eng. J. 2022, 446, 137094.
Wang, C.; Qi, L. M. Heterostructured inter-doped ruthenium-cobalt oxide hollow nanosheet arrays for highly efficient overall water splitting. Angew. Chem., Int. Ed. 2020, 59, 17219–17224.
Hu, F.; Zhu, S. L.; Chen, S. M.; Li, Y.; Ma, L.; Wu, T. P.; Zhang, Y.; Wang, C. M.; Liu, C. C.; Yang, X. J. et al. Amorphous metallic NiFeP: A conductive bulk material achieving high activity for oxygen evolution reaction in both alkaline and acidic media. Adv. Mater. 2017, 29, 1606570.
Li, R. C.; Hu, B. H.; Yu, T. W.; Chen, H. X.; Wang, Y.; Song, S. Q. Insights into correlation among surface–structure–activity of cobalt-derived pre-catalyst for oxygen evolution reaction. Adv. Sci. 2020, 7, 1902830.
Xue, H. Y.; Meng, A. L.; Zhang, H. Q.; Lin, Y. S.; Li, Z. J.; Wang, C. S. 3D urchin like V-doped CoP in situ grown on nickel foam as bifunctional electrocatalyst for efficient overall water-splitting. Nano Res. 2021, 14, 4173–4181.
Li, A.; Zhang, L.; Wang, F. Z.; Zhang, L.; Li, L.; Chen, H. M.; Wei, Z. D. Rational design of porous Ni-Co-Fe ternary metal phosphides nanobricks as bifunctional electrocatalysts for efficient overall water splitting. Appl. Catal. B: Environ. 2022, 310, 121353.
Su, H.; Song, S. J.; Li, S. S.; Gao, Y. Q.; Ge, L.; Song, W. Y.; Ma, T. Y.; Liu, J. High-valent bimetal Ni3S2/Co3S4 induced by Cu doping for bifunctional electrocatalytic water splitting. Appl. Catal. B: Environ. 2021, 293, 120225.
Zhang, Y. Q.; Liu, H. B.; Ge, R. Y.; Yang, J.; Li, S. A.; Liu, Y.; Feng, L. Y.; Li, Y.; Zhu, M. Y.; Li, W. X. Mo-induced in-sttu architecture of NixCoyP/Co2P heterostructure nano-networks on nickel foam as bifunctional electrocatalysts for overall water splitting. Sustainable Mater. Techno. 2022, 33, e00461.
Kang, Y.; Wang, S.; Zhu, S. Q.; Gao, H. X.; Hui, K. S.; Yuan, C. Z.; Yin, H.; Bin, F.; Wu, X. L.; Mai, W. J. et al. Iron-modulated nickel cobalt phosphide embedded in carbon to boost power density of hybrid sodium-air battery. Appl. Catal. B: Environ 2021, 285, 119786.
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This work was financially supported by the National Natural Science Foundation of China (Nos. 21965035 and 22065034) and Sponsored by Natural Science Foundation of Xinjiang Uygur Autonomous Region (No. 2022D01E36).
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Zhao, T., Xu, G., Gong, B. et al. Electronic modulation of sprout-shaped NiCoP nanoarrays by N and Ce doping for efficient overall water splitting. Nano Res. 17, 282–289 (2024). https://doi.org/10.1007/s12274-023-5769-9
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DOI: https://doi.org/10.1007/s12274-023-5769-9