以剥离密排六方结构(HCP)的块状金属,形成单层金属薄膜为切入点,通过用卤素原子钝化中间金属层的方法,形成了一类稳定的ABAB堆叠的金属卤素化合物.对比了*O中吸附O原子和不吸附O原子的Mo-d投影态密度图,期望揭示电子排布、成键状态与材料催化性能之间的关联.电子结构计算表明Mo2X2和W2X2具有很好的导电性.通过与过渡金属二硫化物(MoS2)类比,将缺陷工程(卤素原子空位)引入活性位点,然后计算了其在四电子转移析氧反应中的反应能垒,发现它们具有良好的催化性能,其中,W2Cl2的析氧催化性能最好,过电位仅有1.95 V.最后,通过详细分析电子、轨道之间耦合作用,给出了清晰的物理图像.
Starting from stripping the bulk metal of the hexagonal close-packed( HCP )crystal structure and forming a single-layer metal film, a stable ABAB-stacked metal halide compound was formed by passivating the intermediate metal layer with halogen atoms. The Mo-d projected density of states of adsorbed O atoms and non-adsorbed O atoms in *O are compared, and it is expected to reveal the relationship between electron arrangement, bonding state and catalytic performance of materials. Electronic structure calculations show that Mo2X2 and W2X2 have good electrical conductivity. By analogy with transition metal disulfides( MoS2 ), defect engineering( halogen atom vacancies )is introduced into active sites, and then their reaction energy barriers in the four-electron transfer oxygen evolution reaction are calculated. It is found that they have good catalytic performance. Among them, W2Cl2 has the best oxygen evolution catalytic performance, and the overpotential is only 1.95 V. Finally, a clear physical image is given by analyzing the coupling between electrons and orbits in detail.
[1] LIU Z R, HU J J, GAO F X, et al. Biodegradable and resilient poly(propylene carbonate)based foam from high pressure CO2 foaming[J]. Polym Degrad Stab, 2019, 165: 12-19. DOI: 10.1016/j.polymdegradstab.2019.04.019.
[2] POUDEL M B, KIM A R, RAMAKRISHAN S, et al. Integrating the essence of metal organic framework-derived ZnCoTe-N-C/MoS2 cathode and ZnCo-NPS-N-CNT as anode for high-energy density hybrid supercapacitors[J]. Compos Part B Eng, 2022, 247: 110339. DOI: 10.1016/j.compositesb.2022.110339.
[3] GAO L K, CUI X, SEWELL C D, et al. Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction[J]. Chem Soc Rev, 2021, 50(15): 8428-8469. DOI: 10.1039/d0cs00962h.
[4] RAY A, SULTANA S, PARAMANIK L, et al. Recent advances in phase, size, and morphology-oriented nanostructured nickel phosphide for overall water splitting[J]. J Mater Chem A, 2020, 8(37): 19196-19245. DOI: 10.1039/D0TA05797E.
[5] YUE C W, WANG L C, WANG H H, et al. First-principles study on the electrocatalytic oxygen evolution reaction on the(110)surfaces of layered double hydroxides[J]. J Phys Chem C, 2022, 126(43): 18351-18365. DOI: 10.1021/acs.jpcc.2c07086.
[6] RAVEENDRAN A, CHANDRAN M, DHANUSURAMAN R. A comprehensive review on the electrochemical parameters and recent material development of electrochemical water splitting electrocatalysts[J]. RSC Adv, 2023, 13(6): 3843-3876. DOI: 10.1039/d2ra07642j.
[7] WU Q N, WANG Y N, ZHANG K X, et al. Advances and status of anode catalysts for proton exchange membrane water electrolysis technology[J]. Mater Chem Front, 2023, 7(6): 1025-1045. DOI: 10.1039/D3QM00010A.
[8] SELVAM N C S, DU L J, XIA B Y, et al. Reconstructed water oxidation electrocatalysts: the impact of surface dynamics on intrinsic activities[J]. Adv Funct Materials, 2021, 31(12): 2008190. DOI: 10.1002/adfm.202008190.
[9] CHATENET M, POLLET B G, DEKEL D R, et al. Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments[J]. Chem Soc Rev, 2022, 51(11): 4583-4762. DOI: 10.1039/D0CS01079K.
[10] EDE S R, LUO Z P. Tuning the intrinsic catalytic activities of oxygen-evolution catalysts by doping: a comprehensive review[J]. J Mater Chem A, 2021, 9(36): 20131-20163. DOI: 10.1039/D1TA04032D.
[11] DENG Q, SUN Y, WANG J, et al. Boosting OER performance of IrO2 in acid via urchin-like hierarchical-structure design[J]. Dalton Trans, 2021, 50(18): 6083-6087. DOI: 10.1039/D1DT00329A.
[12] WANG Y, YANG R, DING Y J, et al. Unraveling oxygen vacancy site mechanism of Rh-doped RuO2 catalyst for long-lasting acidic water oxidation[J]. Nat Commun, 2023, 14(1): 1412. DOI: 10.1038/s41467-023-37008-8.
[13] JOHNSON D, PRANADA E, YOO R, et al. Review and perspective on transition metal electrocatalysts toward carbon-neutral energy[J]. Energy Fuels, 2023, 37(3): 1545-1576. DOI: 10.1021/acs.energyfuels.2c03378.
[14] GUO B R, HUO H H, ZHUANG Q X, et al. Iron oxyhydroxide: structure and applications in electrocatalytic oxygen evolution reaction[J]. Adv Funct Materials, 2023, 33(25): 2300557. DOI: 10.1002/adfm.202300557.
[15] GAO L K, CUI X, SEWELL C D, et al. Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction[J]. Chem Soc Rev, 2021, 50(15): 8428-8469. DOI: 10.1039/d0cs00962h.
[16] SUN T, TANG Z Y, ZANG W J, et al. Ferromagnetic single-atom spin catalyst for boosting water splitting[J]. Nat Nanotechnol, 2023, 18(7): 763-771. DOI: 10.1038/s41565-023-01407-1.
[17] GAN J Y, LI F H, TANG Y R, et al. Theoretical study of transition-metal-modified Mo2CO2 MXene as a catalyst for the hydrogen evolution reaction[J]. ChemSusChem, 2020, 13(22): 6005-6015. DOI: 10.1002/cssc.202002163.
[18] LI Z, QI Z Y, WANG S W, et al. In situ formed Pt3Ti nanoparticles on a two-dimensional transition metal carbide(MXene)used as efficient catalysts for hydrogen evolution reactions[J]. Nano Lett, 2019, 19(8): 5102-5108. DOI: 10.1021/acs.nanolett.9b01381.
[19] WANG X, ZHANG Y W, SI H N, et al. Single-atom vacancy defect to trigger high-efficiency hydrogen evolution of MoS2[J]. J Am Chem Soc, 2020, 142(9): 4298-4308. DOI: 10.1021/jacs.9b12113.
[20] KRESSE G, FURTHMüLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Phys Rev B Condens Matter, 1996, 54(16): 11169-11186. DOI: 10.1103/physrevb.54.11169.
[21] PERDEW J P, WANG Y. Accurate and simple analytic representation of the electron-gas correlation energy[J]. Phys Rev B Condens Matter, 1992, 45(23): 13244-13249. DOI: 10.1103/physrevb.45.13244.
[22] BLÖCHL P E. Projector augmented-wave method[J]. Phys Rev B, 1994, 50(24): 17953-17979. DOI: 10.1103/physrevb.50.17953.
[23] MONKHORST H J, PACK J D. Special points for Brillouin-zone integrations[J]. Phys Rev B, 1976, 13(12): 5188-5192. DOI: 10.1103/physrevb.13.5188.
[24] ZANG Y, LU D Q, WANG K, et al. A pyrolysis-free Ni/Fe bimetallic electrocatalyst for overall water splitting[J]. Nat Commun, 2023, 14(1): 1792. DOI: 10.1038/s41467-023-37530-9.
[25] LI Y G, WANG H L, XIE L M, et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction[J]. J Am Chem Soc, 2011, 133(19): 7296-7299. DOI: 10.1021/ja201269b. (
