团簇Ni_3CoP催化析氢活性研究
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摘要
基于密度泛函理论(density functional theory,DFT),在B3LYP/lanl2dz水平下对团簇Ni3CoP的初始构型进行单、三重态下的计算得到优化构型,依据前线轨道理论(frontier molecular orbital theory,FMO)着重通过分析前线轨道图以及比较前线轨道能级差对团簇Ni3CoP催化水析出氢气时的反应机理进行理论研究,结果表明:团簇Ni3CoP通过其最高占据分子轨道(highest occupied molecular orbital,HOMO)与水分子最低未占分子轨道(lowest unoccupied molecular orbital,HUMO)间的电子流动完成氢原子的吸附,且三重态构型在与水分子作用时,其β-HOMO轨道在反应中起主导作用。三重态构型在吸附氢原子后其促进解吸过程析出氢气的催化活性显著下降,而唯一的单重态构型1(1)不仅能在与水分子反应吸附氢原子的过程中展现出较好的催化效果,其在解吸过程中更是表现出了远好于其他三重态构型的催化能力。
Based on density functional theory(DFT),the primary structures of cluster Ni_3CoP were optimized in singlet and triplet under B3 LYP/lanl2 dz level.According to the frontier molecular orbital theory(FMO),the mechanism of the hydrogen evolution reaction catalyzed by cluster Ni_3CoP was studied theoretically from aspects of the frontier molecular orbital images and the difference between the frontier molecular orbital energy levels.Results showed that cluster Ni_3CoP adsorbs H atom through electrons flowing from the highest occupied molecular orbital(HOMO)of cluster Ni_3CoP to the lowest unoccupied molecular orbital(LUMO)of H2 O.As for configurations in triplet,β-HOMO plays a prominent role in the reaction;however,their catalytic properties can descend apparently in the desorption of H atom to generate H2.Nevertheless,structure 1(1),the only configuration in singlet,can not only perform relatively good catalytic capability in adsorbing H atom from H2 O but also improve the desorption process greatly compared with other configurations in triplet.
Based on density functional theory(DFT),the primary structures of cluster Ni_3CoP were optimized in singlet and triplet under B3 LYP/lanl2 dz level.According to the frontier molecular orbital theory(FMO),the mechanism of the hydrogen evolution reaction catalyzed by cluster Ni_3CoP was studied theoretically from aspects of the frontier molecular orbital images and the difference between the frontier molecular orbital energy levels.Results showed that cluster Ni_3CoP adsorbs H atom through electrons flowing from the highest occupied molecular orbital(HOMO)of cluster Ni_3CoP to the lowest unoccupied molecular orbital(LUMO)of H2 O.As for configurations in triplet,β-HOMO plays a prominent role in the reaction;however,their catalytic properties can descend apparently in the desorption of H atom to generate H2.Nevertheless,structure 1(1),the only configuration in singlet,can not only perform relatively good catalytic capability in adsorbing H atom from H2 O but also improve the desorption process greatly compared with other configurations in triplet.
引文
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[2] AHN S H,MANTHIRAM A.Direct growth of ternary Ni-Fe-P porous nanorods onto nickel foam as a highly active,robust bi-functional electrocatalyst for overall water splitting[J].Journal of Materials Chemistry A,2017,5(6):2496-2503.
[3] KANG M,ZHANG Y,LI H Z.Study on the performances of Ni-Co-P/BN(h)nanocomposite coatings made by jet electrodeposition[J].Procedia CIRP,2018,68:221-226.
[4] LI B,ZHANG W.Electrochemical deposition of Ni-Co/SiC nanocomposite coatings for marine environment[J].International Journal of Electrochemical Science,2017,12(8):7017-7030.
[5] SHARMA S,SHARMA S,SHARMA A,et al.Co-deposition of synthesized ZnO nanoparticles into Ni-P matrix using electroless technique and their corrosion study[J].Journal of Materials Engineering and Performance,2016,25(10):4383-4393.
[6] SATHISHKUMAR A,KUMAR M A,PRABU D V,et al.Investigation of wear behaviour properties of electroless Ni-Co-P ternary alloy coating[J].International Journal of Scientific Research in Science,Engineering and Technology,2017,3(1):16-22.
[7] YUAN J,WANG J,GAO Y,et al.Preparation and magnetic properties of Ni-Co-P-Ce coating by electroless plating on silicon substrate[J].Thin Solid Films,2017,632:1-9.
[8] EL-SAYED A H,HEMEDA O M,TAWFIK A,et al.Superior values of the initial permeability for electrodeposited Ni-Co-P-BaFe12O19composite films[J].Phase Transitions,2017,90(4):325-334.
[9] GAO Y,WANG J,YUAN J,et al.Preparation and magnetic properties of Ni-P-La coating by electroless plating on silicon substrate[J].Applied Surface Science,2016,364:740-746.
[10] WU C,WANG K,LI D,et al.Tuning microstructure and magnetic properties of electrodeposited CoNiP films by high magnetic field annealing[J].Journal of Magnetism and Magnetic Materials,2016,416:61-65.
[11] HOU C C,LI Q,WANG C J,et al.Ternary Ni-Co-P nanoparticles as noble-metal-free catalysts to boost the hydrolytic dehydrogenation of ammonia-borane[J].Energy and Environmental Science,2017,10(8):1770-1776.
[12] ZHANG P,CHEN H, WANG M,et al.Gas-templating of hierarchically structured Ni-Co-P for efficient electrocatalytic hydrogen evolution[J].Journal of Materials Chemistry A,2017,5(16):7564-7570.
[13] QIN Z,CHEN Y,HUANG Z,et al.A bifunctional NiCoP-based core/shell cocatalyst to promote separate photocatalytic hydrogen and oxygen generation over graphitic carbon nitride[J].Journal of Materials Chemistry A,2017,5(36):19025-19035.
[14] PAN Y,CHEN Y,LIN Y,et al.Cobalt nickel phosphide nanoparticles decorated carbon nanotubes as advanced hybrid catalysts for hydrogen evolution[J].Journal of Materials Chemistry A,2016,4(38):14675-14686.
[15] FENG Y,YU X Y,PAIK U.Nickel cobalt phosphides quasi-hollow nanocubes as an efficient electrocatalyst for hydrogen evolution in alkaline solution[J].Chemical Communications,2016,52(8):1633-1636.
[16] LI J,WEI G,ZHU Y,et al.Hierarchical NiCoP nanocone arrays supported on Ni foam as an efficient and stable bifunctional electrocatalyst for overall water splitting[J].Journal of Materials Chemistry A,2017,5(28):14828-14837.
[17] HU E,FENG Y,NAI J,et al.Construction of hierarchical Ni-Co-P hollow nanobricks with oriented nanosheets for efficient overall water splitting[J].Energy and Environmental Science,2018,11(4):872-880.
[18] BECK A.Density-functional thermochemistry.III.The role of exact exchange[J].The Journal of Chemical Physics,1993,98(7):5648-5652.
[19] HAY P J,WADT W R.Ab initio effective core potentials for molecular calculations[J].The Journal of Chemical Physics,1985,82(1):299-310.
[20] FANG Z G,HU H Z,GUO J X.Quantum chemical study on geometry and property of cluster Ni4P[J].Chinese Journal of Structural Chemistry,2006,25(1):7-16.
[21] WEI Z D,YAN A Z,FENG Y C,et al.Study of hydrogen evolution reaction on Ni-P amorphous alloy in the light of experimental and quantum chemistry[J].Electrochemistry Communications,2007,9(11):2709-2715.
[22] FUKUI K,YONEZAWA T,SHINGU H.A molecular orbital theory of reactivity in aromatic hydrocarbons[J].Journal of Chemical Physics,1952,20(10):1653
[23]李雯博,方志刚,赵振宁,等.团簇Co5B2反应活性的DFT研究[J].广西师范大学学报(自然科学版),2017,35(4):76-83.
[24] FUKUI K.Recognition of stereochemical paths by orbital interaction[J].Accounts of Chemical Research,1971,4(2):57-64.