原位生成非晶纳米钴高效催化氨硼烷的醇解制氢（英文）
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摘要
用金属钴配合物和过渡金属(Cu,Ni,Co等)原位生成的非晶纳米粒子作为均相、多相催化剂,研究氨硼烷的醇解放氢反应,结果发现原位生成的非晶钴纳米粒子展现出优异的产氢性能。通过10次的催化循环测试,钴纳米粒子放氢催化转换数(TON)可达6 000,最高催化产氢速率(TOF)达515 mol_(H_2)·mol_(metal)~(-1)·h~(-1)。该催化剂制备方便,且产氢稳定性好。此外,对钴纳米粒子催化氨硼烷放氢实验做动力学研究,计算其催化活化能为20.00 kJ·mol~(-1),低于大多数已经报道的其他纳米催化剂催化氨硼烷放氢反应的活化能。通过硼谱的跟踪检测,发现钴纳米催化氨硼烷的醇解反应产物是硼酸三甲酯,并对此催化反应机理进行了初步的解释和讨论。
Amorphous Co nanoparticles formed in-situ displayed high catalytic activity for hydrogen generation from the methanolysis reaction of ammonia borane, among many homogeneous catalysts and heterogeneous catalysts of cobalt. Its turnover number(TON) was up to 6 000 for ten cycles and its turnover frequency(TOF) was up to 515mol_(H_2)·mol_(metal)~(-1)·h~(-1). Moreover, the easily preparation and the great recycling performance made it have good application in future. After the kinetics studies, its catalytic activation energy(Ea) for the methanolysis reaction was measured as 20.00 kJ·mol~(-1), which was lower than most of the reported values for other nano-sized catalysts.Through the ~(11)B NMR, trimethylborate was the only product. Furthermore, the catalytic reaction mechanism was preliminarily explained and discussed.
Amorphous Co nanoparticles formed in-situ displayed high catalytic activity for hydrogen generation from the methanolysis reaction of ammonia borane, among many homogeneous catalysts and heterogeneous catalysts of cobalt. Its turnover number(TON) was up to 6 000 for ten cycles and its turnover frequency(TOF) was up to 515mol_(H_2)·mol_(metal)~(-1)·h~(-1). Moreover, the easily preparation and the great recycling performance made it have good application in future. After the kinetics studies, its catalytic activation energy(Ea) for the methanolysis reaction was measured as 20.00 kJ·mol~(-1), which was lower than most of the reported values for other nano-sized catalysts.Through the ~(11)B NMR, trimethylborate was the only product. Furthermore, the catalytic reaction mechanism was preliminarily explained and discussed.
引文
[1]Esswein A J, Nocera D G. Chem. Rev., 2007,107:4022-4047
[2]Osterloh F E. Chem. Soc. Rev., 2013,42:2294-2320
[3]Yadav M, Xu Q. Energy Environ. Sci., 2012,5:9698-9725
[4]Hu C G, Chen X Y, Dai Q B, et al. Nano Energy, 2017,41:367-376
[5]Xu Y F, Mao N, Feng S, et al. Macromol. Chem. Phys., 2017,218:1700049
[6]Xing Y L, Fang B Z, Bonakdarpour A, et al. Int. J. Hydrogen Energy, 2014,39:7859-7867
[7]Zhang H, Cai J M, Wang Y T, et al. Appl. Catal. B, 2018,220:126-136
[8]Khalid N R, Liaqat M, Tahir M B, et al. Ceram. Int., 2018,44:546-549
[9]Xu Y X, Chen R T, Li Z, et al. ACS Appl. Mater. Interfaces,2017,9:23230-23237
[10]Aw V D B, Areán C O. Chem. Commun., 2008,6:668-681
[11]Grewe T, Meggouh M, Tüysüz H. Chem. Asian J., 2016,11:22-42
[12]Sun D H, Mazumder V, Metin?, et al. ACS Nano, 2011,5:6458-6464
[13]Chen W Y, Ji J, Duan X Z, et al. Chem. Commun., 2014,50:2142-2144
[14]Zhang R Z, Zheng J L, Chen T W, et al. J. Alloys Compd.,2018,763:538-545
[15]Ramachandran P V, Gagare P D. Inorg. Chem., 2007,46:7810-7817
[16]?zhava D,?zkar S. Mol. Catal., 2017,439:50-59
[17]Cui L, Cao X Y, Sun X P, et al. ChemCatChem, 2018,10:1-7
[18]?zhava D,?zkar S. Appl. Catal. B, 2018,237:1012-1020
[19]Karatas Y, Gülcan M,?elebi M, et al. ChemistrySelect, 2017,2:9628-9635
[20]Kalidindi S B, Vernekar A A, Jagirdar B R. Phys. Chem.Chem. Phys., 2009,11:770-775
[21]Zhao B H, Liu J Y, Zhou L T, et al. Appl. Surf. Sci., 2016,362:79-85
[22]Ke D D, Li Y, Wang J, et al. Int. J. Hydrogen Energy, 2016,41:2564-2574
[23]Bulut A, Yurderi M, Ertas E, et al. Appl. Catal. B, 2016,180:121-129
[24]Ramachandran P V, Drolet M P. Tetrahedron Lett., 2018,59:967-970
[25]KorytiakováE, Thiel N O, Pape F, et al. Chem. Commun.,2017,53:732-735
[26]Fu S M, Chen N Y, Liu X F, et al. J. Am. Chem. Soc., 2016,138:8588-8594
[27]Chandra M, Xu Q. J. Power Sources, 2007,168:135-142
[28]Chen W Y, Ji J, Feng X, et al. J. Am. Chem. Soc., 2014,136:16736-16739
[29]Luo S P, Mejia E, Friedrich A, et al. Angew. Chem. Int. Ed.,2013,52:419-423
[30]Paine R T, Narula C K. Chem. Rev., 1990,90:73-91
[31]Yu J, Bai H B, Wang J, et al. New J. Chem., 2013,37:366-372
[32]Surviliene S. Solid State Ionics, 2008,179:222-227
[33]Dai H B, Kang X D, Wang P. Int. J. Hydrogen Energy, 2010,35:10317-10323
[34]Qiu X Q, Wu X, Wu Y W, et al. RSC Adv., 2016,6:106211-106217
[35]Sun D H, Mazumder V, Metin?, et al. ACS Catal., 2012,2:1290-1295
[36]Filiz B C, Figen A K, Piskin S. Appl. Catal. A, 2018,550:320-330
[37]Cao S W, Jiang J, Zhu B C, et al. Phys. Chem. Chem. Phys.,2016,18:19457-19463
[38]Liu S, Li Y, Shen W J. Chin. J. Catal., 2015,36:1409-1418
[39]Li Y, Dai Y, Tian X K. Int. J. Hydrogen Energy, 2015,40:9235-9243
[40]Metin?,?zkar S. Energy Fuels, 2009,23:3517-3526
[41]Xu Q, Chandra M. J. Power Sources, 2006,163:364-370
[2]Osterloh F E. Chem. Soc. Rev., 2013,42:2294-2320
[3]Yadav M, Xu Q. Energy Environ. Sci., 2012,5:9698-9725
[4]Hu C G, Chen X Y, Dai Q B, et al. Nano Energy, 2017,41:367-376
[5]Xu Y F, Mao N, Feng S, et al. Macromol. Chem. Phys., 2017,218:1700049
[6]Xing Y L, Fang B Z, Bonakdarpour A, et al. Int. J. Hydrogen Energy, 2014,39:7859-7867
[7]Zhang H, Cai J M, Wang Y T, et al. Appl. Catal. B, 2018,220:126-136
[8]Khalid N R, Liaqat M, Tahir M B, et al. Ceram. Int., 2018,44:546-549
[9]Xu Y X, Chen R T, Li Z, et al. ACS Appl. Mater. Interfaces,2017,9:23230-23237
[10]Aw V D B, Areán C O. Chem. Commun., 2008,6:668-681
[11]Grewe T, Meggouh M, Tüysüz H. Chem. Asian J., 2016,11:22-42
[12]Sun D H, Mazumder V, Metin?, et al. ACS Nano, 2011,5:6458-6464
[13]Chen W Y, Ji J, Duan X Z, et al. Chem. Commun., 2014,50:2142-2144
[14]Zhang R Z, Zheng J L, Chen T W, et al. J. Alloys Compd.,2018,763:538-545
[15]Ramachandran P V, Gagare P D. Inorg. Chem., 2007,46:7810-7817
[16]?zhava D,?zkar S. Mol. Catal., 2017,439:50-59
[17]Cui L, Cao X Y, Sun X P, et al. ChemCatChem, 2018,10:1-7
[18]?zhava D,?zkar S. Appl. Catal. B, 2018,237:1012-1020
[19]Karatas Y, Gülcan M,?elebi M, et al. ChemistrySelect, 2017,2:9628-9635
[20]Kalidindi S B, Vernekar A A, Jagirdar B R. Phys. Chem.Chem. Phys., 2009,11:770-775
[21]Zhao B H, Liu J Y, Zhou L T, et al. Appl. Surf. Sci., 2016,362:79-85
[22]Ke D D, Li Y, Wang J, et al. Int. J. Hydrogen Energy, 2016,41:2564-2574
[23]Bulut A, Yurderi M, Ertas E, et al. Appl. Catal. B, 2016,180:121-129
[24]Ramachandran P V, Drolet M P. Tetrahedron Lett., 2018,59:967-970
[25]KorytiakováE, Thiel N O, Pape F, et al. Chem. Commun.,2017,53:732-735
[26]Fu S M, Chen N Y, Liu X F, et al. J. Am. Chem. Soc., 2016,138:8588-8594
[27]Chandra M, Xu Q. J. Power Sources, 2007,168:135-142
[28]Chen W Y, Ji J, Feng X, et al. J. Am. Chem. Soc., 2014,136:16736-16739
[29]Luo S P, Mejia E, Friedrich A, et al. Angew. Chem. Int. Ed.,2013,52:419-423
[30]Paine R T, Narula C K. Chem. Rev., 1990,90:73-91
[31]Yu J, Bai H B, Wang J, et al. New J. Chem., 2013,37:366-372
[32]Surviliene S. Solid State Ionics, 2008,179:222-227
[33]Dai H B, Kang X D, Wang P. Int. J. Hydrogen Energy, 2010,35:10317-10323
[34]Qiu X Q, Wu X, Wu Y W, et al. RSC Adv., 2016,6:106211-106217
[35]Sun D H, Mazumder V, Metin?, et al. ACS Catal., 2012,2:1290-1295
[36]Filiz B C, Figen A K, Piskin S. Appl. Catal. A, 2018,550:320-330
[37]Cao S W, Jiang J, Zhu B C, et al. Phys. Chem. Chem. Phys.,2016,18:19457-19463
[38]Liu S, Li Y, Shen W J. Chin. J. Catal., 2015,36:1409-1418
[39]Li Y, Dai Y, Tian X K. Int. J. Hydrogen Energy, 2015,40:9235-9243
[40]Metin?,?zkar S. Energy Fuels, 2009,23:3517-3526
[41]Xu Q, Chandra M. J. Power Sources, 2006,163:364-370