电解水制氢是实现清洁能源转化的有效途径,其中析氧反应(OER)作为电解水的阳极反应,对整体能耗起关键作用。然而,OER的反应动力学较为缓慢,且通常需要贵金属催化剂(如RuO2或者IrO2)来降低过电位,这显著提高了制氢成本,限制了电解水制氢技术的大规模应用。因此,开发高效、稳定且低成本的非贵金属OER催化剂成为研究重点。以普鲁士蓝类似物为模板,通过高温退火法制备了Co3O4@Pt复合催化剂。采用扫描电子显微镜、透射电子显微镜、X射线衍射仪、X射线光电子能谱仪对复合催化剂的结构和形貌进行表征,通过电化学工作站测试了其催化性能。结果表明:Co3O4@Pt具有多孔纳米立方体结构,形成了Pt和Co3O4的异质结界面,提供了快速的电荷传输路径;Co3O4@Pt在低过电位下实现了高电流密度,同时表现出较低的塔菲尔斜率和更高的双电层电容,表明其具有丰富的活性位点和优异的OER动力学。基于以上优势,该催化剂有效提高了电荷转移效率,降低了OER反应能垒,从而提升了电解水效率。
Hydrogen production through water electrolysis is an effective pathway for clean energy conversion,in which the oxygen evolution reaction (OER),as the anode reaction of water electrolysis,plays a critical role in determining the overall energy consumption.However,the reaction kinetics of OER are relatively sluggish and it typically requires precious metal catalysts (such as RuO2 or IrO2) to reduce the overpotential,which significantly increases the cost of hydrogen production and limits its large-scale application.Therefore,it is urgent to develop efficient,stable,and low-cost non-precious metal OER catalysts.In this work,the composite catalyst Co3O4@Pt was rationally prepared using Prussian blue analogs (Co3[Co(CN)6]3) as templates via a high-temperature annealing method.The structure and morphology of the composite catalyst were characterized by scanning electron microscopy (SEM),transmission electron microscopy (TEM),X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS),and its catalytic performance was tested by an electrochemical workstation.The results showed that the resulting Co3O4@Pt exhibited a porous cubic structure,forming a heterojunction interface between Pt and Co3O4,which provided a fast charge transfer pathway for OER.Electrochemical tests demonstrated that Co3O4@Pt achieved high current density at low overpotentials,along with a lower Tafel slope and higher double-layer capacitance,indicating abundant active sites and excellent OER kinetics.Based on these advantages,the catalyst greatly improved the charge transfer,reduced the reaction energy barrier,and thereby enhanced the catalytic activity toward water electrolysis.
[1] Zhu Y M,Klingenhof M,Gao C,et al.Facilitating alkaline hydrogen evolution reaction on the hetero-interfaced Ru/RuO2 through Pt single atoms doping[J].Nature Communications,2024,15(1):1447.
[2] Wang M Y,Feng X F,Li S,et al.Spinel-type metal oxides with tailored amorphous/crystalline heterointerfaces for enhanced electrocatalytic water splitting[J].Advanced Functional Materials,2024,34(51):2410439.
[3] Huang S S,Jin Z Q,Ding Y W,et al.Encapsulating Fe2O3 nanotubes into carbon-coated Co9S8 nanocages derived from a MOFs-directed strategy for efficient oxygen evolution reactions and Li-ions storage[J].Small,2021,17(51):2103178.
[4] Wu H F,Yin K,Qi W H,et al.Rapid fabrication of Ni/NiO@CoFe layered double hydroxide hierarchical nanostructures by femtosecond laser ablation and electrodeposition for efficient overall water splitting[J].Chemsuschem,2019,12(12):2773-2779.
[5] Srinivas K,Chen Y F,Su Z,et al.Heterostructural CoFe2O4/CoO nanoparticles-embedded carbon nanotubes network for boosted overall water-splitting performance[J].Electrochimica Acta,2022,404:139745.
[6] Zhang X,Liu R R,Zang Y P,et al.Co/CoO nanoparticles immobilized on Co-N-doped carbon as trifunctional electrocatalysts for oxygen reduction,oxygen evolution and hydrogen evolution reactions[J].Chemical Communications,2016,52(35):5946-5949.
[7] Gao Y,Zhang N,Wang C R,et al.Construction of Fe2O3@CuO heterojunction nanotubes for enhanced oxygen evolution reaction[J].ACS Applied Energy Materials,2020,3(1):666-674.
[8] Dai T Y,Zhang X,Sun M Z,et al.Uncovering the promotion of CeO2/CoS1.97 heterostructure with specific spatial architectures on oxygen evolution reaction[J].Advanced Materials,2021,33(42):2102593.
[9] Wei Y,Zheng M B,Zhu W,et al.Hollow structures prussian blue,its analogs,and their derivatives:synthesis and electrochemical energy-related applications[J].Carbon Neutralization,2023,2(3):271-299.
[10] Mule A R,Ramulu B,Yu J S.Prussian-blue analogue-derived hollow structured Co3S4/CuS2/NiS2 nanocubes as an advanced battery-type electrode material for high-performance hybrid supercapacitors[J].Small,2022,18(10):2105185.
[11] Meng Z Y,Qiu Z M,Shi Y X,et al.Micro/nano metal-organic frameworks meet energy chemistry:a review of materials synthesis and applications[J].eScience,2023,3(2):100092.
[12] Huang S S,Wang H T,Wang S D,et al.Encapsulating CoS2-CoSe2 heterostructured nanocrystals in N-doped carbon nanocubes as highly efficient counter electrodes for dye-sensitized solar cells[J].Dalton Transactions,2018,47(15):5236-5244.
[13] Yang M,Ning Q L,Fan C Y,et al.Large-scale Ni-MOF derived Ni3S2 nanocrystals embedded in N-doped porous carbon nanoparticles for high-rate Na+ storage[J].Chinese Chemical Letters,2021,32(2):895-899.
[14] Cui Z X,Lin J X,Wu J H,et al.N-doped CoP nanoparticles embedded in electrospun N-doped porous carbon nanofiber as high-efficiency oxygen evolution electrocatalysts[J].Journal of Alloys and Compounds,2021,854:156830.
[15] Zhang K E,Sun P T,Huang Y L,et al.Electrochemical nitrate reduction to ammonia on CuCo nanowires at practical level[J].Advanced Functional Materials,2024,34(44):2405179.
[16] Zhang M L,Song K P,Liu C,et al.Electron-rich Au nanocrystals/Co3O4 interface for enhanced electrochemical nitrate reduction into ammonia[J].Journal of Colloid and Interface Science,2023,650:193-202.
[17] Wu S L,Jing Y Y,Luo W J,et al.Ag-Co3O4-CoOOH-nanowires tandem catalyst for efficient electrocatalytic conversion of nitrate to ammonia at low overpotential via triple reactions[J].Advanced Science,2023,10(33):2303789.
[18] Zhang J K,Chen C Q,Chen S,et al.Highly dispersed Pt nanoparticles supported on carbon nanotubes produced by atomic layer deposition for hydrogen generation from hydrolysis of ammonia borane[J].Catalysis Science & Technology,2017,7(2):322-329.
[19] Zhang H,Wang J,Qin F Q,et al.V-doped Ni3N/Ni heterostructure with engineered interfaces as a bifunctional hydrogen electrocatalyst in alkaline solution:simultaneously improving water dissociation and hydrogen adsorption[J].Nano Research,2021,14(10):3489-3496.
[20] Zhu M,Xu H Y,Dai J,et al.A dynamically stable self-assembled CoFe (oxy)hydroxide-based nanocatalyst with boosted electrocatalytic performance for the oxygen-evolution reaction[J].Journal of Materials Chemistry A,2024,12(36):24308-24317.
[21] Gong T Y,Zhang J Y,Liu Y,et al.Construction of hetero-phase Mo2C-CoO@N-CNFs film as a self-supported Bi-functional catalyst towards overall water splitting[J].Chemical Engineering Journal,2023,451:139025.
基金资助
国家自然科学基金区域创新发展联合基金项目(U24A20286);江苏省科技成果转化基金项目(BA2023020)
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