期刊
ACS CATALYSIS
卷 8, 期 5, 页码 4132-4142出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b04347
关键词
electrocatalysis; greenhouse gas; heterogeneous catalyst; modified electrodes; ethylene; DFT; blue moon
资金
- Engineering and Physical Sciences Research Council (EPSRC) [EP/N009525/1]
- Welsh Government Ser Cymru Program
- European Regional Development Fund (ERDF) through the Welsh Government
- European Union Horizon research and innovation program under the Marie Sklodowska-Curie grant [663830]
- Ser Cymru II Welsh Fellowship - European Regional Development Fund (ERDF)
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
- Holland Computing Center at the University of Nebraska Lincoln
- EPSRC [EP/N009525/1] Funding Source: UKRI
A strategy to modulate the electrocatalytic activity of copper toward CO, reduction involving adsorption of acrylamide, acrylic acid, and allylamine polymers is presented. Modification of electrodeposited copper foam with poly(acrylamide) leads to a significant enhancement in faradaic efficiency for ethylene from 13% (unmodified foam) to 26% at -0.96 V vs RHE, whereas methane yield is unaffected. Effects from crystalline phase distribution and copper oxide phases are ruled out as the source of enhancement through XPS and in situ XRD analysis. DFT calculations reveal that poly(acrylamide) adsorbs on the copper surface via the oxygen atom on the carbonyl groups and enhances ethylene formation by (i) charge donation to the copper surface that activates CO for dimerization, (ii) chemical stabilization of the CO dimer (a key intermediate for C-2 products) by hydrogen-bond interactions with the -NH2 group, and (iii) facilitating the adsorption of CO molecules near the polymer, increasing local surface coverage. Poly(acrylamide) with copper acts as a multipoint binding catalytic system where the interplay between activation and stabilization of intermediates results in enhanced selectivity toward ethylene formation. Modification with poly(acrylic acid) which has a similar structure to poly(acrylamide) also shows some enhancement in activity but is unstable, whereas poly(allylamine) completely suppresses CO2 reduction in favor of the hydrogen evolution reaction.
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