电催化氮气还原反应(NRR)因可在常温常压下高效固氮而被认为是一种前景广阔的合成氨的方法,有望替代传统Haber-Bosch工艺。电催化剂的设计和制备是提升NRR性能的关键因素。采用水热法制备了金属-有机框架材料(MOF),通过高温热处理获得MOF衍生的片状Ni/C纳米材料,将其用于NRR反应的电催化剂。研究发现,在0.1mol/L KOH电解液中,电位为-0.9V时Ni/C纳米材料最大的氨产率为66.57μg/(h·mg),法拉第效率高达33.67%,且显示了良好的电化学稳定性。
Electrocatalytic nitrogen reduction reaction (NRR) is considered to be a very promising way to prepare ammonia due to its efficient nitrogen fixation at room temperature and pressure,and is expected to replace the conventional Haber-Bosch process.The design and synthesis of electrocatalyst is a key factor to improve the performances of NRR.Metal organic framework material (MOF) was prepared via hydrothermal method,and the sheet-like MOF-derived Ni/C nanomaterial was further acquired by high-temperature heat treatment and was utilized as electrocatalyst of NRR.The research results showed that the Ni/C had a maximum ammonia yield of 66.57μg/(h·mg) at -0.9V in 0.1mol/L KOH electrolyte solution.The Faraday efficiency was as high as 33.67%,which presented good electrochemical stability.
[1] Chen G F,Ren S Y,Zhang L L,et al.Advances in electrocatalytic N2 reduction—strategies to tackle the selectivity challenge[J].Small Methods,2018,3(6):1800337-1800356.
[2] Niu L J,An L,Wang X Y,et al.Effect on electrochemical reduction of nitrogen to ammonia under ambient conditions:challenges and opportunities for chemical fuels[J].Journal of Energy Chemistry,2021,61:304-318.
[3] Deng J,Iñiguez J A,Liu C.Electrocatalytic nitrogen reduction at low temperature[J].Joule,2018,2(5):846-856.
[4] Shi L,Yin Y,Wang S B,et al.Rational catalyst design for N2 reduction under ambient conditions:strategies toward enhanced conversion efficiency[J].ACS Catalysis,2020,10(12):6870-6899.
[5] Duan G Y,Chen Y M,Tang Y,et al.Advances in electrocatalytic ammonia synthesis under mild conditions[J].Progress in Energy and Combustion Science,2020,81:100860-100889.
[6] Cui X Y,Tang C,Zhang Q.A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions[J].Advanced Energy Materials,2018,8(22):1800369-1800393.
[7] Tang C,Qiao S Z.How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully[J].Chemical Society Reviews,2019,48(12):3166-3180.
[8] Patil S B,Wang D Y.Exploration and investigation of periodic elements for electrocatalytic nitrogen reduction[J].Small,2020,16(45):2002885-2002928.
[9] Zhu X J,Mou S Y,Peng Q L,et al.Aqueous electrocatalytic N2 reduction for ambient NH3 synthesis:recent advances in catalysts developing and performances boosting[J].Journal of Materials Chemistry A,2020,8(4):1545-1556.
[10] Li Y B,Liu Y P,Wang J,et al.Plasma-engineered NiO nanosheets with enriched oxygen vacancies for enhanced electrocatalytic nitrogen fixation[J].Inorganic Chemistry Frontiers,2020,7(2):455-463.
[11] Yang H R,Luo D,Gao R,et al.Reduction of N2 to NH3 by TiO2-supported Ni cluster catalysts:a DFT study[J].Physical Chemistry Chemical Physics,2021,23(31):16707-16717.
[12] Wang Y,Tian Y J,Zhang J F,et al.Tuning morphology and electronic structure of amorphous NiFeB nanosheets for enhanced electrocatalytic N2 reduction[J].ACS Applied Energy Materials,2020,3(10):9516-9522.
[13] Wang J,Jang H,Li G K,et al.Efficient electrocatalytic conversion of N2 to NH3 on NiWO4 under ambient conditions[J].Nanoscale,2020,12(3):1478-1483.
[14] Wang X H,Wang J,Li Y B,et al.Nitrogen-doped NiO nanosheet array for boosted electrocatalytic N2 reduction[J].ChemCatChem,2019,11(18):4529-4536.
[15] Zhang L,Ding Y R,Li R R,et al.Ni-based metal-organic framework derived Ni@C nanosheets on a Ni foam substrate as a supersensitive non-enzymatic glucose sensor[J].Journal of Materials Chemistry B,2017,5(28):5549-5555.
[16] Yang X X,Sun S,Meng L,et al.Molecular single iron site ca-talysts for electrochemical nitrogen fixation under ambient conditions[J].Applied Catalysis B:Environmental,2021,285:119794-119802.
[17] Watt G W,Chrisp J D.A spectrophotometric method for the determination of hydrazine[J].Analytical Chemistry,1952,24:2006-2008.
[18] Chen Q Q,Zhang X D,Jin Y W,et al.An overview on noble metal (group Ⅷ)-based heterogeneous electrocatalysts for nitrogen reduction reaction[J].Chemistry-An Asian Journal,2020,15(24):4131-4152.
[19] Zhang X,Qu N,Yang S X,et al.Shape-controlled synthesis of Ni-based metal-organic frameworks with albizia flower-like spheres@nanosheets structure for high performance supercapacitors[J].Journal of Colloid and Interface Science,2020,575:347-355.
[20] Song Y X,Qiang T T,Ye M,et al.Metal organic framework derived magnetically separable 3-dimensional hierarchical Ni@C nanocomposites:synthesis and adsorption properties[J].Applied Surface Science,2015,359:834-840.
[21] Cheng H,Ding L X,Chen G F,et al.Molybdenum carbide nanodots enable efficient electrocatalytic nitrogen fixation under ambient conditions[J].Advanced Materials,2018,30(46):1803694-1803700.
[22] Qiu W B,Xie X Y,Qiu J D,et al.High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst[J].Nature Communications,2018,9:3485-3492.
[23] Li L Q,Tang C,Xia B Q,et al.Two-dimensional mosaic bismuth nanosheets for highly selective ambient electrocatalytic nitrogen reduction[J].ACS Catalysis,2019,9(4):2902-2908.
[24] Chen Y J,Wu B,Sun B L,et al.N-doped porous carbon self-generated on nickel oxide nanosheets for electrocatalytic N2 fixation with a faradaic efficiency beyond 30%[J].ACS Sustainable Chemistry & Engineering,2019,7(23):18874-18883.
[25] Jiang X L,He M,Tang M Y,et al.Nanostructured bimetallic Ni-Fe phosphide nanoplates as an electrocatalyst for efficient N2 fixation under ambient conditions[J].Journal of Materials Science,2020,55:15252-15262.
[26] Luo S J,Li X M,Gao W G,et al.An MOF-derived C@NiO@Ni electrocatalyst for N2 conversion to NH3 in alkaline electrolytes[J].Sustainable Energy & Fuels,2020,4(1):164-170.
[27] Wu X K,Wang Z C,Han Y,et al.Chemically coupled NiCoS/C nanocages as efficient electrocatalysts for nitrogen reduction reactions[J].Journal of Material Chemistry A,2020,8(2):543-547.
[28] Zhang R,Han J R,Zheng B Z,et al.Metal-organic framework-derived shuttle-like V2O3/C for electrocatalytic N2 reduction under ambient conditions[J].Inorganic Chemistry Frontiers,2019,6(2):391-395.
[29] Mukherjee S,Cullen D A,Karakalos S,et al.Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N2 and H2O in alkaline electrolytes[J].Nano Energy,2018,48:217-226.
[30] Zhang Z Q,Yao K D,Cong L C,et al.Facile synthesis of a Ru-dispersed N-doped carbon framework catalyst for electrochemical nitrogen reduction[J].Catalysis Science & Techno-logy,2020,10(5):1336-1342.
[31] Song Z X,Zhang L,Davis K D,et al.Recent advances in MOF-derived single atom catalysts for electrochemical applications[J].Advanced Energy Materials,2020,10(38):2001561-2001602.
[32] Luo S J,Li X M,Zhang B H,et al.MOF-derived Co3O4@NC with core-shell structures for N2 electrochemical reduction under ambient conditions[J].ACS Applied Materials & Interfaces,2019,11(30):26891-26897.
基金资助
国家自然科学基金(21573025,21773018)
PDF
