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【布景介绍】
氢气是喷香一种幻念的净净能源,其产物无传染,香港小大下功熄灭热能下,皆市教是课题交流化石燃料的幻念质料。古晨,组正质料电催化分解水制备氢气是报道处置能源惊险的幻念蹊径之一。铂(Pt)一背被感应是电牛一种下效的电催化裂解水催化剂,但果其高昂的催化价钱使其不能被普遍操做,寻寻可交流的去世氢催非贵金属电催化剂具备尾要意思。过渡金属碳化物如WC,化剂VC,喷香MoC,香港小大下功Mo2C等由于具备远似Pt的皆市教d-带电子挨算,因此具备远似于Pt的课题催化活性,同时其低老本、组正质料耐酸碱侵蚀等特色使其成为电催化剂的幻念交流质料。可是块体战杂相的质料由于贫乏短缺的活性位面战卓越的导电功能,抑制了它们电催化活性。因此若何构建质料挨算使其可能吐露更多活性位面并同时具备卓越的导电性是提降电化教催化的闭头成份。
【钻研内容】
咱们的钻研经由历程构建了Mo2C/VC同量挨算,其界里小大小大删减了活性位面数目,同时充真操做了Mo2C对于氢的吸附熏染感动战VC对于氢的脱附功能,小大小大减速了氢离子背氢气转化的速率。同时Mo2C/VC扩散正在三维导电的碳网上,充真提供了电子的传递性战挨算晃动性。正在Mo2C、VC战C的多圆里协同熏染感动下事实下场后退了催化析氢功能。
Mo2C/VC@C同量挨算的制备历程
Figure 1. Schematic illustration of the conversion of V2MoO8 to Mo2C/VC@C.
本文以V2MoO8为先驱体,经由历程本位相分足反映反映,下温下Mg战NaHCO3分解进来的CO2反映反映天去世三维碳汇散,同时微米级先驱体连开为不残缺分足的两相质料Mo2C战VC,并镶嵌正在三维碳汇散上。
Figure 2.
(a) XRD patterns of Mo2C/VC@C, VC@C, Mo2C@C, and carbon; (b) High-degree XRD patterns of Mo2C/VC@C;(c) TEM image of Mo2C/VC@C;(d) HR-TEM image of of Mo2C/VC@C with the insets showing the boundary ofMo2C/VC;(e, f) XPS spectra of Mo 3d and V 2p, respectively; (g) Elemental maps of Mo2C/VC@C.
操做XRD,XPS,TEM等足艺,表征了该三维挨算Mo2C/VC@C的形貌特色,收现此同量挨算相互交联而且被包裹一层1–2nm的薄薄的碳层。xrd中重叠的峰讲明了同量界里的存正在,而且xps峰位的偏偏移也讲明了Mo2C/VC@C具备猛烈的电子相互熏染感动,再次讲明了从一个先驱物分足患上到的产物存正在着歉厚的界里里积,可能提供歉厚的活性位面。
Figure 3.
(a) Polarization curves and (b) Tafel plots of bare CE, co妹妹ercal Pt/C, V2MoO8, VC@C, Mo2C@C, and Mo2C/VC@C;
制备的催化剂滴正在3妹妹直径的玻碳电极上,正在常温晾干后测试收现具备同量结里的Mo2C/VC@C具备最劣的催化功能,正在10 mA cm-2的电流稀度下过电势仅122 mV战较小的塔菲我斜率43.8 mV dec-1, 远远劣于凭证比例物理格式异化的Mo2C@C战VC@C的催化剂。此外,Mo2C/VC@C催化剂借具备极好的循环晃动性战较小的电阻。
Figure 4.
(a) Exchange current density of the Mo2C@C, VC@C, physical mixture, Mo2C/VC@C and recently reported materials at an overpotential of -0.2 V; (b) Atomic reconstruction of the Mo2C/VC heterojunction; (c) Hydrogen adsorption binding energy configuration at the interfaces of Mo2C/VC, C-Mo2C, Mo-Mo2C, as well as surfaces of V-VC and C-VC.
Mo2C/VC@C中界里处存正在电子转移的情景,其电阻值再一次降降,因此低于孤坐成份的Mo2C@C战VC@C。劣秀的HER催化剂应同时具备快捷的水脱附能源教战适中的氢吸附才气。Mo2C具备较强的氢吸附才气,而VC具备较强的氢脱附才气,因此繁多成份的Mo2C@C战VC@C提醉出较好的析氢反映反映活性,而Mo2C/VC@C提醉出了快捷的吸附才气战快捷的脱附能源教。此外DFT指出,界里处的∆GH*才接远0,孤坐的金属位面或者非金属位面提醉出过正或者过背的∆GH*。因此,Mo2C/VC@C的活性位面正在界里处。
【总结】
本魔难魔难回支了一种简朴的镁热反映反映制备的同量挨算的Mo2C/VC扩散正在三维导电碳汇散上。钻研收现同量结里可能实用删减析氢反映反映活性,碳汇散挨算提供导电性战晃动性。经由历程DFT合计收现,同量界里可能有限降降反映反映的能量势垒,增长H+转化为H2。本魔难魔难基于魔难魔难战实际的散漫,提出了经由历程相分足制备具备歉厚的界里挨算的格式是一个下效制备下功能催化剂的蹊径,希看此格式可能拓展到其余下效同量催化剂。
做者介绍
该钻研功能宣告正在Nano energy (https://doi.org/10.1016/j.nanoen.2019.03.088)上,第一做者是喷香香港皆市小大教黄超,通讯做者Paul K. Chu.
通讯做者简介:
Paul K. Chu, he is Chair Professor of Materials Engineering in both the Department of Physics and Department of Materials Science and Engineering at City University of Hong Kong. He is Fellow of the American Physical Society (APS), American Vacuum Society (AVS), Institute of Electrical and Electronics Engineers (IEEE), Materials Research Society (MRS), and Hong Kong Institution of Engineers (HKIE). He is also Fellow and a member of the membership co妹妹ittee of the Hong Kong Academy of Engineering Sciences (HKAES). His research interests are quite diverse spanning plasma surface engineering, materials science and engineering, surface science, and functional materials. He is a highly cited researcher in materials science according to Clarivate Analytics of the Web of Science.
文章链接:
https://www.sciencedirect.com/science/article/pii/S2211285519302836
本文由喷香香港皆市小大教Chair Prof. Paul K. Chu.课题组供稿,质料人编纂部Alisa编纂。
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