采用静电纺丝技术制备了一种纤维状钴铜双金属氧化物催化剂,并考察了催化剂中不同金属比例、不同催化剂制备方法、催化剂加入量、氨硼烷加入量以及水解温度对氨硼烷水解释氢的影响。结果表明:由于钴和铜之间存在强的协同效应,从而提高了催化剂的催化性能。当钴和铜的摩尔比为8∶1时,所制备的催化剂Co8Cu1Ox-NF性能最优,催化氨硼烷水解的活化能为38.41kJ/mol,反应转化频率(TOF)为2443.52mL/(min·gmetal),经过5次循环使用仍能保持较高的催化活性,该催化剂对氨硼烷水解具有良好的催化活性和循环稳定性。
A fibrous cobalt-copper bimetal oxide catalyst was fabricated by electrospinning technique.The effects of different metal molar ratios in the catalyst,catalyst preparation methods,catalyst dosages,ammonia borane amounts,and reaction temperatures on the hydrolytic dehydrogenation of ammonia borane were investigated.The results showed that the catalytic performance of the catalyst was improved due to the strong synergistic effect between cobalt and copper.When the molar ratio of cobalt to copper was 8∶1,the catalyst Co8Cu1Ox-NF had the best performance.For the hydrolysis of ammonia borane over the Co8Cu1Ox-NF catalyst,the turnover frequency (TOF) reached 2443.52mL/(min·gmetal) and the activation energy (Ea) was 38.41kJ/mol.The catalyst still remained high catalytic activity after 5 cycles and exhibited superior catalytic activity and recycling stability in the hydrolysis of ammonia borane.
[1] Jiao W,Hu X,Ren H.Magnetic Ni and Ni/Pt hollow nanospheres and their catalytic activities for hydrolysis of ammonia borane[J].Journal of Material Chemistey A,2014,43:18171-18176.
[2] Wei W,Wang Z,Xu J,et al.Cobalt hollow nanospheres:controlled synthesis,modification and highly catalytic performance for hydrolysis of ammonia borane[J].Science Bulletin,2017,5:326-331.
[3] Peng Yumei,He Yating,Wang Yi,et al.Sustainable one-pot construction of oxygen-rich nitrogen-doped carbon nanosheets stabilized ultrafine Rh nanoparticles for efficient ammonia borane hydrolysis[J].Journal of Colloid and Interface Science,2021,594:131-140.
[4] Zhang J,Dong Y N,Liu Q X,et al.Hierarchically alloyed Pd-Cu microarchitecture with tunable shapes:morphological engineering,and catalysis for hydrogen evolution reaction of ammonia borane[J].International Journal of Hydrogen Energy,2019,44(57):30226-30236.
[5] Hasegawa M,Sato S,Yanaba K,et al.Autoantibodies against phosphatidylserine-prothrombin complex in patients with systemic sclerosis[J].Annals of the Rheumatic Diseases,2004,63(11):1514-1517.
[6] Rakap M,Kalu E E,Ozkar S.Hydrogen generation from hydrolysis of ammonia-borane using Pd-PVB-TiO2 and Co-Ni-P/Pd-TiO2 under stirred conditions[J].Journal of Power Sources,2012,210:184-190.
[7] Liu H,Xu C,Lu R,et al.Efficient hydrogen evolution from ammonia borane hydrolysis with Rh decorated on phosphorus-doped carbon[J].International Journal of Hydrogen Energy,2019,44(31):16548-16556.
[8] Dai H B,Kang X D,Wang P.Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane[J].International Journal of Hydrogen Energy,2010,35(19):10317-10323.
[9] Simagina V I,Komova O V,Oerova A M,et al.Cobalt oxide catalyst for hydrolysis of sodium borohydride and ammonia borane[J].Applied Catalysis A:General,2011,394(1-2):86-92.
[10] Guan S,An L,Ashraf S,et al.Oxygen vacancy excites Co3O4 nanocrystals embedded into carbon nitride for accelerated hydrogen generation[J].Applied Catalysis B:Environmental,2020,269:118775.
[11] Liao J,Feng Y,Zhang X,et al.CuO-Co3O4 composite nanoplatelets for hydrolyzing ammonia borane[J].ACS Applied Nano Materials,2021,4(8):7640-7649.
[12] Nadagouda M N,Varma R S.A greener synthesis of core (Fe,Cu)-shell (Au,Pt,Pd,and Ag) nanocrystals using aqueous vitamin C[J].Crystal Growth & Design,2007,7(12):2582-2587.
[13] Sun W,Lu X,Tong Y.A one-pot synthesis of a highly dispersed palladium/polypyrrole/polyacrylonitrile nanofiber membrane and its recyclable catalysis in hydrogen generation from ammonia borane[J].Journal of MSaterial Chemistey A,2014,19:6740-6746.
[14] 郭奥莹,刘贵山,江宇,等.中空多孔ZnO纳米纤维的制备及光催化性能[J].大连工业大学学报,2020,39(4):302-307.
[15] 张旺玺.静电纺丝聚丙烯腈基杂化复合纤维制备及其应用研究现状[J].化工新型材料,2022,50(1):6-11.
[16] Xu D,Ge K,Chen Y,et al.Cable-Like core-shell mesoporous SnO2 nanofibers by single-nozzle electrospinning phase separation for formaldehyde sensing[J].Chemistry-A European Journal,2020,26(42):9365-9370.
[17] Wu H,Zhang R,Liu X,et al.Electrospinning of Fe,Co,and Ni nanofibers:synthesis,assembly,and magnetic properties[J].Chemistry of Materials,2008,14:3506-3511.
[18] 马克伟,朱琳娜,孙丽霞,等.MOF模板法制备Co3O4及其光催化降解罗丹明B[J].水处理技术,2020,46(9):58-62.
[19] 赵志红,张燕娟,黄祖强,等.Cu-Fe@C复合材料的制备及其光芬顿催化降解硝基苯研究[J].现代化工,2022,42(3):123-132.
[20] 邵景景,朱鹏.还原氧化石墨烯/Co3O4复合物的制备[J].黑龙江科技大学学报,2014,24(3):229-232.
[21] Dubal D P,Gund G S,Holze R,et al.Surfactant-assisted morphological tuning of hierarchical CuO thin films for electrochemical supercapacitors[J].Dalton Transactions,2013,42(18):6459-6467.
[22] Liu J,Zhang A,Jiang X,et al.Selective CO2 hydrogenation to hydrocarbons on Cu-promoted Fe-based catalysts:dependence on Cu-Fe interaction[J].ACS Sustainable Chemistry & Engineering,2018,6(8):10182-10190.
[23] Wang W,Zhang Y,Zhang J,et al.Metal-organic framework-derived Cu2O-CuO octahedrons for sensitive and selective detection of ppb-level NO2 at room temperature[J].Sensors and Actuators B:Chemical,2021,328:129045.
[24] Shu T,Wang H,Li Q,et al.Highly stable Co3O4 nanoparticles/carbon nanosheets array derived from flake-like ZIF-67 as an advanced electrode for supercapacacitor[J].Chemical Engineering Journal,2021,419:129631.
[25] Zhang C L,Lu B R,Cao F H,et al.Electrospun metal-organic framework nanoparticle fibers and their derived electrocatalysts for oxygen reduction reaction[J].Nano Energy,2019,55:226-233.
[26] Wang Y,Zou K,Zhang D,et al.Cobalt-copper-boron nanoparticles as catalysts for the efficient hydrolysis of alkaline sodium borohydride solution[J].International Journal of Hydrogen Energy,2020,45(16):9845-9853.
[27] Hang X L,Zhang D X,Chang G G,et al.Bimetallic (Zn/Co) MOFs-derived highly dispersed metallic Co/HPC for completely hydrolytic dehydrogenation of Ammonia-Borane[J].Industrial & Engineering Chemistry Research,2019,58(17):7209-7216.
[28] Yousef A,Barakat N A M,Kim H Y.Electrospun Cu-doped titania nanofibers for photocatalytic hydrolysis of ammonia borane[J].Applied Catalysis A-General,2013,467:98-106.
[29] Arihur E E,Li F,Momade F W Y,et al.Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube[J].Energy,2014,76:822-829.
[30] Wu Y,Wu X,Liu Q,et al.Magnetically recyclable Ni@h-BN composites for efficient hydrolysis of ammonia borane[J].International Journal of Hydrogen Energy,2017,42(25):16003-16011.
[31] Qiu F,Dai Y,Li L,et al.Synthesis of Cu@FeCo core-shell nanoparticles for the catalytic hydrolysis of ammonia borane[J].International Journal of Hydrogen Energy,2014,39(1):436-441.
[32] Xu D,Wang W D,Tian M,et al.Immobilization of Pt nanoparticles in hollow mesoporous silica nanocapsules:an aggregation- and leaching-resistant catalyst[J].Journal of Colloid and Interface Science,2018,516:407-415.
[33] Zhuang D W,Dai H B,Zhong Y J,et al.A new reactivation method towards deactivation of honeycomb ceramic monolith supported cobalt-molybdenum-boron catalyst in hydrolysis of sodium borohydride[J].International Journal of Hydrogen Energy,2015,40(30):9373-9381.
[34] Kim D R,Cho K W,Choi Y I,et al.Fabrication of porous Co-Ni-P catalysts by electrodeposition and their catalytic characteristics for the generation of hydrogen from an alkaline NaBH4 solution[J].International Journal of Hydrogen Energy,2009,34(6):2622-2630.
[35] Wang Y,Qi K Z,Wu S W,et al.Preparation,characterization and catalytic sodium borohydride hydrolysis of nanostructured cobalt-phosphorous catalysts[J].Journal of Power Sources,2015,284:130-137.
基金资助
国家自然科学基金青年基金(21908043)