化工新型材料

化工新型材料 ›› 2025, Vol. 53 ›› Issue (7) : 134-140. DOI: 10.19817/j.cnki.issn1006-3536.2025.07.012

新材料与新技术

ZIF-67衍生的CoP-NS/NCNF自支撑电极的制备及其电催化析氢性能研究

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Preparation of ZIF-67-derived CoP-NS/NCNF self-supporting electrodes and their electrocatalytic hydrogen evolution performance

Ye Yipeng¹, Xu Yangyang¹, Dong Mengjiao¹, Xiong Jiabin², Wei Ye³, Li Bingxin³

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Received		Published
2024-06-24		2025-07-20
Issue Date	Revised Date
2025-07-22	2024-06-24

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摘要

采用静电纺丝技术和溶剂热反应法,在静电纺聚丙烯腈纳米纤维上原位生长Co(OH)₂纳米片,采用固态熔融法将Co(OH)₂纳米片转化为ZIF-67纳米片,最后通过低温磷化法,得到ZIF-67衍生的CoP纳米片包覆氮掺杂碳纳米纤维(NCNF)自支撑电极(记作CoP-NS/NCNF)。采用扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪、拉曼光谱仪和X射线光电子能谱仪对自支撑电极进行表征与分析,并进行电催化析氢性能测试。结果表明:基于ZIF-67衍生的碳骨架和CoP以及纳米片阵列结构,制备的CoP-NS/NCNF自支撑电极作为催化剂时表现出优异的析氢反应催化性能。在1mol/L KOH溶液中,电流密度达到10mA/cm²时过电位仅为103mV,塔菲尔斜率为86mV/dec,明显优于Co(OH)₂衍生的CoP包覆碳纳米纤维(CoP/NCNF)自支撑电极(过电位为146mV,塔菲尔斜率为95mV/dec)。此外,经过12h计时电流和1000次循环测试后,CoP-NS/NCNF电流密度、线性扫描伏安曲线和形貌均未发生明显变化,表现出良好的循环稳定性和耐久性。

Abstract

In this work,Co(OH)₂ nanosheets were in-situ grown on electrospun PAN nanofibers by electrospinning technology and solvothermal reaction method,and the Co(OH)₂ nanosheets were converted into ZIF-67 nanosheets by solid-state melting method.A CoP-NS/NCNF self-supporting electrode with ZIF-67-derived cobalt phosphide nanosheets anchored on nitrogen-doped carbon nanofibers (NCNF) was obtained by low-temperature phosphating treatment finally.The morphology and structure of the self-supporting electrode were characterized and analyzed by scanning electron microscopy (SEM),X-ray diffraction (XRD),Fourier transform infrared spectroscopy (FT-IR),Raman spectroscopy,and X-ray photoelectron spectroscopy (XPS).The electrocatalytic hydrogen evolution performance was also tested.The results showed that,based on the ZIF-67-derived carbon skeleton and CoP,as well as the nanosheet array structure,the prepared CoP-NS/NCNF self-supporting electrode exhibited excellent catalytic hydrogen evolution performance when used as a catalyst.The overpotential at a current density of 10mA/cm² was only 103mV in 1mol/L KOH solution,and the tafel slope was 86mV/dec,which was significantly better than that of Co(OH)₂-derived CoP/NCNF self-supporting electrode (overpotential of 146mV and Tafel slope of 95mV/dec).In addition,there were no significant changes in current density,LSV polarization curve,and morphology of CoP-NS/NCNF after 12 h of current-time testing and 1000 cycles of CV testing,demonstrating excellent cycling stability and durability.

关键词

静电纺纳米纤维 / ZIF-67 / 磷化钴 / 纳米片 / 析氢反应

Key words

electrospun nanofibers / ZIF-67 / cobalt phosphide / nanosheets / hydrogen evolution reaction

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ZIF-67衍生的CoP-NS/NCNF自支撑电极的制备及其电催化析氢性能研究[J]. 化工新型材料, 2025, 53(7): 134-140 DOI:10.19817/j.cnki.issn1006-3536.2025.07.012

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参考文献

原文顺序 | 出版日期 | 本文引用

[1] Liu S J,Cheng H Y,Zhao F Y,et al.Controllable synthesis of VSB-5 microspheres and microrods:growth mechanism and selective hydrogenation catalysis[J].Chemistry,2008,14(13):4074-4081.
[2] Liu B,Zhong B,Li F,et al.Co₂P/CoP heterostructures with significantly enhanced performance in electrocatalytic hydrogen evolution reaction:synthesis and electron redistribution mechanism[J].Nano Research,2023,16(11):12830-12839.
[3] Ding X,Yu J,Huang W,et al.Modulation of the interfacial charge density on Fe₂P-CoP by coupling CeO₂ for accelerating alkaline electrocatalytic hydrogen evolution reaction and overall water splitting[J].Chemical Engineering Journal,2023,451:138550.
[4] Li J,Hu J,Zhang M,et al.A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution[J].Nature Communications,2021,12(1):3502.
[5] Liu T,Li P,Yao N,et al.CoP-doped MOF-bbased electrocatalyst for pH-universal hydrogen evolution reaction[J].Angewandte Chemie International Edition,2019,58(14):4679-4684.
[6] Pei A,Xie R,Zhang Y,et al.Effective electronic tuning of Pt single atomsviaheterogeneous atomic coordination of (Co,Ni)(OH)₂ for efficient hydrogen evolution[J].Energy & Environmental Science,2023,16(3):1035-1048.
[7] Afarinandeh A,Heidari K,Barczak M,et al.Controlled removal of fluoride by ZIF-8,ZIF-67,and Ni-MOF of different morphologies[J].Arabian Journal of Chemistry,2023,16(7):104837.
[8] Boppella R,Tan J,Yang W,et al.Homologous CoP/NiCoP heterostructure on N-doped carbon for highly efficient and pH-universal hydrogen evolution electrocatalysis[J].Advanced Functional Materials,2018,29(6):1807976.
[9] Li Y,Li H,Cao K,et al.Electrospun three dimensional Co/CoP@nitrogen-doped carbon nanofibers network for efficient hydrogen evolution[J].Energy Storage Materials,2018,12:44-53.
[10] Zhou Q,Sun R,Ren Y,et al.Reactive template-derived interfacial engineering of CoP/CoO heterostructured porous nanotubes towards superior electrocatalytic hydrogen evolution[J].Carbon Energy,2023,5(1):273.
[11] Luo Y,Li X,Cai X,et al.Two-dimensional MoS₂ confined Co(OH)₂ electrocatalysts for hydrogen evolution in alkaline electrolytes[J].ACS Nano,2018,12(5):4565-4573.
[12] Shen S,Wang Z,Lin Z,et al.Crystalline-amorphous interfaces coupling of CoSe₂/CoP with optimized d-band center and boosted electrocatalytic hydrogen evolution[J].Advanced Materials,2022,34(13):2110631.
[13] Sun J,Ren G,Qin S,et al.Reconstruction Co-O-Mo in amorphous-crystalline MoO_x/Co(OH)₂ interface for industry-level active and stable electrocatalytic seawater hydrogen evolution[J].Nano Energy,2024,121:109246.
[14] Wang H,Wang Y,Zhang J,et al.Electronic structure engineering through Fe-doping CoP enables hydrogen evolution coupled with electro-Fenton[J].Nano Energy,2021,84:105943.
[15] Wang M,Liu X,Wu X.Realizing efficient electrochemical overall water electrolysis through hierarchical CoP@NiCo-LDH nanohybrids[J].Nano Energy,2023,114:108681.
[16] Shooshtari Gugtapeh H,Rezaei M.One-step electrodeposition of a mesoporous Ni/Co-imidazole-based bimetal-organic framework on pyramid-like NiSb with abundant coupling interfaces as an ultra-stable heterostructural electrocatalyst for water splitting[J].ACS Applied Materials & Interfaces,2023,15(29):34682-34697.
[17] Zhang H,Wu Y,Wang X,et al.The construction of defect-rich CoP@CoP@(Co/Ni)₂P triple-shell hollow nanospheres with boosted electrocatalytic hydrogen evolution perfor-mances over a wide pH range[J].Chemical Engineering Journal,2023,463:142448.
[18] Zhang K,Jia J,Yang E,et al.Work-function-induced electron rearrangement of in-plane FeP@CoP heterojunction enhances all pH range and alkaline seawater hydrogen evolution reaction[J].Nano Energy,2023,114:108601.
[19] Zhang S,Zhang S,Song L,et al.A general approach to the synthesis of metal phosphide catalysts[J].Powder Technology,2014,253:509-513.
[20] Zhu J,Chi J,Wang X,et al.Boosting hydrogen evolution reaction activity of Ru anchored binary oxyhydroxide by F-doping in alkaline seawater[J].Nano Energy,2024,121:109249.
[21] You B,Jiang N,Sheng M,et al.High-performance overall water splitting electrocatalysts derived from cobalt-based metal-organic frameworks[J].Chemistry of Materials,2015,27(22):7636-7642.

基金资助

国家留学基金委地方合作项目(202208410324);河南省高等学校重点研发项目(23A430008,24A540005);河南省重点研发与推广专项(科技攻关)指导项目(222102230047);中国纺织工业联合会科技指导项目(2021047);2023年第一批教育部产学合作协同育人项目(230800383251919,230825135207276);河南省大学生创新创业计划训练项目(202410465050,202410465060,202410465072);中原工学院学科实力提升计划“学科青年硕导培育计划”项目(SD202210);中原工学院青年骨干教师项目(2024XQG05,2024XQG06)

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