In situ growth of phosphorized ZIF-67-derived amorphous CoP/Cu₂O@CF electrocatalyst for efficient hydrogen evolution reaction

Abstract

Transition metal phosphides have been extensively studied for catalytic applications in water splitting. Herein, we report an in situ phosphorization of zeolitic imidazole frameworks (ZIF-67) to generate amorphous cobalt phosphide/ZIF-67 heterojunction on a self-supporting copper foam (CF) substrate with excellent performance for hydrogen evolution reaction (HER). The needle-leaf like copper hydroxide was anchored on CF surface, which acted as implantation to grow ZIF-67. The intermediate product was phosphorized to obtain final electrocatalyst (CoP/Cu₂O@CF) with uniform particle size, exhibiting a rhombic dodecahedron structure with wrinkles on the surface. The electrochemical measurement proved that CoP/Cu₂O@CF catalyst exhibited excellent HER activity and long-term stability in 1.0 mol·L^–1 KOH solution. The overpotential was only 62 mV with the Tafel slope of 83 mV·dec^–1 at a current density of 10 mA·cm^–2, with a large electrochemical active surface area. It also showed competitive performance at large current which indicated the potential application to industrial water electrolysis to produce hydrogen. First-principle calculations illustrated that benefit from the construction of CoP/ZIF-67 heterojunction, the d-band center of CoP downshifted after bonding with ZIF-67 and the Gibbs free energy (ΔG_H*) changed from –0.18 to –0.11 eV, confirming both decrease in overpotential and excellent HER activity. This work illustrates the efficient HER activity of CoP/Cu₂O@CF catalyst, which will act as a potential candidate for precious metal electrocatalysts.

Key words： CoP/Cu₂O@CF; electrocatalyst; phosphorization; HER; DFT

Conflict of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 41573103) and the Shandong Natural Science Foundation (Grant Nos. ZR2021MB049, ZR2022QB211) of China.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2320-1 and is accessible for authorized users.

References

1 Zhang X. The development trend of and suggestions for China’s hydrogen energy industry. Engineering, 2021, 7(6): 719–721

2 Wang J, Gao Y, Kong H, Kim J, Choi S, Ciucci F, Hao Y, Yang S, Shao Z, Lim J. Non-precious-metal catalysts for alkaline water electrolysis: operando characterizations, theoretical calculations, and recent advances. Chemical Society Reviews, 2020, 49(24): 9154–9196

3 Cheng N, Stambula S, Wang D, Banis M N, Liu J, Riese A, Xiao B, Li R, Sham T K, Liu L M, Botton G A, Sun X. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nature Communications, 2016, 7(1): 13638

4 Shi Y, Zhang B. Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction. Chemical Society Reviews, 2016, 45(6): 1529–1541

5 Liang H, Liu J. Insights on the corrosion and degradation of MXenes as electrocatalysts for hydrogen evolution reaction. ChemCatChem, 2022, 14(6): e202101375

6 Theerthagiri J, Murthy A P, Lee S J, Karuppasamy K, Arumugam S R, Yu Y, Hanafiah M M, Kim H S, Mittal V, Choi M Y. Recent progress on synthetic strategies and applications of transition metal phosphides in energy storage and conversion. Ceramics International, 2021, 47(4): 4404–4425

7 Jiang Y, Lu Y, Lin J, Wang X, Shen Z. Water splitting: a hierarchical MoP nanoflake array supported on Ni foam: a bifunctional electrocatalyst for overall water splitting. Small Methods, 2018, 2(5): 1800028

8 Wang R, Dong X Y, Du J, Zhao J Y, Zang S Q. MOF-derived bifunctional Cu₃P nanoparticles coated by a N,P-codoped carbon shell for hydrogen evolution and oxygen reduction. Advanced Materials, 2018, 30(6): 1703711

9 Liu T, Liu D, Qu F, Wang D, Zhang L, Ge R, Hao S, Ma Y, Du G, Asiri A M, Chen L, Sun X. Enhanced electrocatalysis for energy-efficient hydrogen production over CoP catalyst with nonelectroactive Zn as a promoter. Advanced Energy Materials, 2017, 7(15): 1700020

10 Guan C, Xiao W, Wu H, Liu X, Zang W, Zhang H, Ding J, Feng Y P, Pennycook S J, Wang J. Hollow Mo-doped CoP nanoarrays for efficient overall water splitting. Nano Energy, 2018, 48: 73–80

11 Guan C, Wu H, Ren W, Yang C, Liu X, Ouyang X, Song Z, Zhang Y, Pennycook S J, Cheng C, Wang J. Metal−organic framework-derived integrated nanoarrays for overall water splitting. Journal of Materials Chemistry A, 2018, 6(19): 9009–9018

12 Suo N, Han X, Chen C, He X, Dou Z, Lin Z, Cui L, Xiang J. Engineering vanadium phosphide by iron doping as bifunctional electrocatalyst for overall water splitting. Electrochimica Acta, 2020, 333: 135531

13 Wang S, McGuirk C M, d’Aquino A, Mason J A, Mirkin C A. Metal−organic framework nanoparticles. Advanced Materials, 2018, 30(37): 1800202

14 He T, Kong X J, Li J R. Chemically stable metal−organic frameworks: rational construction and application expansion. Accounts of Chemical Research, 2021, 54(15): 3083–3094

15 Jadhav H S, Bandal H A, Ramakrishna S, Kim H. Critical review, recent updates on zeolitic imidazolate framework-67 (ZIF-67) and its derivatives for electrochemical water splitting. Advanced Materials, 2022, 34(11): e2107072

16 Kharissova O V, Kharisov B I, Ulyand I E, García T H. Catalysis using metal−organic framework-derived nanocarbons: recent trends. Journal of Materials Research, 2020, 35(16): 2190–2207

17 Zhai Y, Ren X, Yan J, Liu S. High density and unit activity integrated in amorphous catalysts for electrochemical water splitting. Small Structures, 2020, 2(4): 2000096

18 Guo C, Shi Y, Lu S, Yu Y, Zhang B. Amorphous nanomaterials in electrocatalytic water splitting. Chinese Journal of Catalysis, 2021, 42(8): 1287–1296

19 Anantharaj S, Noda S. Amorphous catalysts and electrochemical water splitting: an untold story of harmony. Small, 2020, 16(2): e1905779

20 Yang M, Jiang Y, Qu M, Qin Y, Wang Y, Shen W, He R, Su W, Li M. Strong electronic couple engineering of transition metal phosphides-oxides heterostructures as multifunctional electrocatalyst for hydrogen production. Applied Catalysis B: Environmental, 2020, 269: 118803

21 Wang Z, Xiao B, Lin Z, Xu Y, Lin Y, Meng F, Zhang Q, Gu L, Fang B, Guo S, Zhong W. PtSe₂/Pt heterointerface with reduced coordination for boosted hydrogen evolution reaction. Angewandte Chemie International Edition, 2021, 60(43): 23388–23393

22 Yu Z, Li Y, Martin-Diaconescu V, Simonelli L, Ruiz Esquius J, Amorim I, Araujo A, Meng L, Faria J L, Liu L. Highly efficient and stable saline water electrolysis enabled by self-supported nickel-iron phosphosulfide nanotubes with heterointerfaces and under-coordinated metal active sites. Advanced Functional Materials, 2022, 32(38): 2206138

23 Zhang L, Zheng Y, Wang J, Geng Y, Zhang B, He J, Xue J, Frauenheim T, Li M. Ni/Mo bimetallic-oxide-derived heterointerface-rich sulfide nanosheets with Co-doping for efficient alkaline hydrogen evolution by boosting volmer reaction. Small, 2021, 17(10): e2006730

24 Inta H R, Ghosh S, Mondal A, Tudu G, Koppisetti H V S R M, Mahalingam V. Ni_0.85Se/MoSe₂ interfacial structure: an efficient electrocatalyst for alkaline hydrogen evolution reaction. ACS Applied Energy Materials, 2021, 4(3): 2828–2837

25 Wang T, Tao L, Zhu X, Chen C, Chen W, Du S, Zhou Y, Zhou B, Wang D, Xie C, Long P, Li W, Wang Y, Chen R, Zou Y, Fu X Z, Li Y, Duan X, Wang S. Combined anodic and cathodic hydrogen production from aldehyde oxidation and hydrogen evolution reaction. Nature Catalysis, 2021, 5(1): 66–73

26 Guo X, Xing T, Lou Y, Chen J. Controlling ZIF-67 crystals formation through various cobalt sources in aqueous solution. Journal of Solid State Chemistry, 2016, 235: 107–112

27 Qazi U Y, Javaid R, Tahir N, Jamil A, Afzal A. Design of advanced self-supported electrode by surface modification of copper foam with transition metals for efficient hydrogen evolution reaction. International Journal of Hydrogen Energy, 2020, 45(58): 33396–33406

28 Jiang Y, Liang J, Yue L, Luo Y, Liu Q, Kong Q, Kong X, Asiri A M, Zhou K, Sun X. Reduced graphene oxide supported ZIF-67 derived CoP enables high-performance potassium ion storage. Journal of Colloid and Interface Science, 2021, 604: 319–326

29 Liu H, Guan J, Yang S, Yu Y, Shao R, Zhang Z, Dou M, Wang F, Xu Q. Metal−organic-framework-derived Co₂P nanoparticle/multi-doped porous carbon as a trifunctional electrocatalyst. Advanced Materials, 2020, 32(36): e2003649

30 Zhang X, Zheng R, Jin M, Shi R, Ai Z, Amini A, Lian Q, Cheng C, Song S. NiCoS_x@cobalt carbonate hydroxide obtained by surface sulfurization for efficient and stable hydrogen evolution at large current densities. ACS Applied Materials & Interfaces, 2021, 13(30): 35647–35656

31 Yang H, Chen Z, Guo P, Fei B, Wu R. B-doping-induced amorphization of LDH for large-current-density hydrogen evolution reaction. Applied Catalysis B: Environmental, 2020, 261: 118240

32 Shan X, Liu J, Mu H, Xiao Y, Mei B, Liu W, Lin G, Jiang Z, Wen L, Jiang L. An engineered superhydrophilic/superaerophobic electrocatalyst composed of the supported CoMoS_x chalcogel for overall water splitting. Angewandte Chemie International Edition, 2020, 59(4): 1659–1665

33 Beltrán-Suito R, Menezes P W, Driess M. Amorphous outperforms crystalline nanomaterials: surface modifications of molecularly derived CoP electro(pre)catalysts for efficient water-splitting. Journal of Materials Chemistry A, 2019, 7(26): 15749–15756

34 Anjum M A R, Okyay M S, Kim M, Lee M H, Park N, Lee J S. Bifunctional sulfur-doped cobalt phosphide electrocatalyst outperforms all-noble-metal electrocatalysts in alkaline electrolyzer for overall water splitting. Nano Energy, 2018, 53: 286–295

35 Zhao Y, Jin B, Zheng Y, Jin H, Jiao Y, Qiao S Z. Charge state manipulation of cobalt selenide catalyst for overall seawater electrolysis. Advanced Energy Materials, 2018, 8(29): 1801926

36 Li J, Xu Y, Liang L, Ge R, Yang J, Liu B, Feng J, Li Y, Zhang J, Zhu M, Li S, Li W. Metal−organic frameworks-derived nitrogen-doped carbon with anchored dual-phased phosphides as efficient electrocatalyst for overall water splitting. Sustainable Materials and Technologies, 2022, 32: e00421

37 Song M, Zhang Z, Li Q, Jin W, Wu Z, Fu G, Liu X. Ni-foam supported Co(OH)F and Co-P nanoarrays for energy-efficient hydrogen production via urea electrolysis. Journal of Materials Chemistry A, 2019, 7(8): 3697–3703

38 Wei C, Sun S, Mandler D, Wang X, Qiao S Z, Xu Z J. Approaches for measuring the surface areas of metal oxide electrocatalysts for determining their intrinsic electrocatalytic activity. Chemical Society Reviews, 2019, 48(9): 2518–2534

39 McCrory C C, Jung S, Peters J C, Jaramillo T F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. Journal of the American Chemical Society, 2013, 135(45): 16977–16987

40 Kitchin J R, Norskov J K, Barteau M A, Chen J G. Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals. Journal of Chemical Physics, 2004, 120(21): 10240–10246

41 Medford A J, Vojvodic A, Hummelshøj J S, Voss J, Abild-Pedersen F, Studt F, Bligaard T, Nilsson A, Nørskov J K. From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis. Journal of Catalysis, 2015, 328: 36–42

42 Jiao S, Fu X, Huang H. Descriptors for the evaluation of electrocatalytic reactions: d-band theory and beyond. Advanced Functional Materials, 2021, 32(4): 2107651