文献类型：期刊文献

英文题名：Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

作者：Liu, Min[1];Pang, Yuanjie[2];Zhang, Bo[1,3];De Luna, Phil[4];Voznyy, Oleksandr[1];Xu, Jixian[1];Zheng, Xueli[1,5];Dinh, Cao Thang[1];Fan, Fengjia[1];Cao, Changhong[2];de Arquer, F. Pelayo Garcia[1];Safaei, Tina Saberi[1];Mepham, Adam[6];Klinkova, Anna[7];Kumacheva, Eugenia[7];Filleter, Tobin[2];Sinton, David[2];Kelley, Shana O.[6,8,9];Sargent, Edward H.[1]

机构：[1]Univ Toronto, Dept Elect & Comp Engn, 35 St George St, Toronto, ON M5S 1A4, Canada;[2]Univ Toronto, Dept Mech & Ind Engn, 5 Kings Coll Rd, Toronto, ON M5S 3G8, Canada;[3]East China Univ Sci & Technol, Dept Phys, 130 Meilong Rd, Shanghai 200237, Peoples R China;[4]Univ Toronto, Dept Mat Sci & Engn, 184 Coll St, Toronto, ON M5S 3E4, Canada;[5]Tianjin Univ, Sch Mat Sci & Engn, Tianjin Key Lab Composite & Funct Mat, Tianjin 300072, Peoples R China;[6]Univ Toronto, Inst Biomat & Biomed Engn, 164 Coll St, Toronto, ON M5S 3G9, Canada;[7]Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada;[8]Univ Toronto, Leslie Dan Fac Pharm, Dept Pharmaceut Sci, 144 Coll St, Toronto, ON M5S 3M2, Canada;[9]Univ Toronto, Dept Biochem, 1 Kings Coll Circle, Toronto, ON M5S 1A8, Canada

年份：2016

卷号：537

期号：7620

起止页码：382

外文期刊名：NATURE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000383098000050)】；

基金：This work was supported by the Ontario Research Fund: Research Excellence programme, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the CIFAR Bio-Inspired Solar Energy programme and a University of Toronto Connaught grant. B.Z. acknowledges funding from Shanghai Municipal Natural Science Foundation (14ZR1410200) and the National Natural Science Foundation of China (21503079). We thank X. Lan, P. Kanjanaboos, G. Walters, L. Levina, R. Wolowiec, D. Kopilovic, E. Palmiano, T. Burdyny and J. Tam from the University of Toronto for Au electron beam deposition, liquid products testing, AFM testing, TEM EELS measurements, discussions and additional aids during the course of study, Y. Tian from the King Abdullah University of Science and Technology for electrode preparation assistance, and M. Bajdich, L. D. Chen and K. Chan from Stanford University for advice on DFT calculations. This work has also benefited from the Spherical Grating Monochromator beamlines at the Canadian Light Source. DFT calculations were performed on the IBM BlueGene Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP).

语种：英文

摘要：Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity(1-7). Unfortunately, the reaction suffers from slow kinetics(7,8) owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species(9,10), but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption(11), but this comes at the cost of increased hydrogen (H-2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.