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How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

ABSTRACT: The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

SUBMITTER: Bachmeier A

PROVIDER: S-EPMC3838662 | biostudies-literature | 2013 Oct

REPOSITORIES: biostudies-literature

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How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

Bachmeier Andreas A Wang Vincent C C VC Woolerton Thomas W TW Bell Sophie S Fontecilla-Camps Juan C JC Can Mehmet M Ragsdale Stephen W SW Chaudhary Yatendra S YS Armstrong Fraser A FA

Journal of the American Chemical Society 20130926 40

The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activit ...[more]

PMID: 24070184

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Project description:Abstract It remains a real challenge to control the selectivity of the electrocatalytic CO2 reduction (eCO2R) reaction to valuable chemicals and fuels. Most of the electrocatalysts are made of non‐renewable metal resources, which hampers their large‐scale implementation. Here, we report the preparation of bimetallic copper‐lead (CuPb) electrocatalysts from industrial metallurgical waste. The metal ions were extracted from the metallurgical waste through simple chemical treatment with ammonium chloride, and CuxPby electrocatalysts with tunable compositions were fabricated through electrodeposition at varying cathodic potentials. X‐ray spectroscopy techniques showed that the pristine electrocatalysts consist of Cu0, Cu1+ and Pb2+ domains, and no evidence for alloy formation was found. We found a volcano‐shape relationship between eCO2R selectivity toward two electron products, such as CO, and the elemental ratio of Cu and Pb. A maximum Faradaic efficiency towards CO was found for Cu9.00Pb1.00, which was four times higher than that of pure Cu, under the same electrocatalytic conditions. In situ Raman spectroscopy revealed that the optimal amount of Pb effectively improved the reducibility of the pristine Cu1+ and Pb2+ domains to metallic Cu and Pb, which boosted the selectivity towards CO by synergistic effects. This work provides a framework of thinking to design and tune the selectivity of bimetallic electrocatalysts for CO2 reduction through valorization of metallurgical waste. Bimetallic Cu‐Pb electrocatalysts were prepared from industrial metallurgical residues and used to electrochemically convert CO2 into valuable chemicals. The metlas were extracted through chemical treatment with ammonium chloride, and Cu−Pb electrocatalysts with varying ratios were prepared through electrodeposition. Compared with pure Cu, the bimetallic catalyst displayed a promotional effect on the conversion of carbon dioxide to carbon monoxide. In situ and ex situ characterization revealed that the interplay between in situ reduced Cu and Pb sites results in boosted CO production through synergistic effects.

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How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

Publications

How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

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