Activation Matters: Hysteresis Effects during Electrochemical Looping of Colloidal Ag Nanowire Catalysts
- Huifang HuHuifang HuDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Huifang Hu
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- Menglong LiuMenglong LiuDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Menglong Liu
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- Ying KongYing KongDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Ying Kong
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- Nisarga MysuruNisarga MysuruDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Nisarga Mysuru
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- Changzhe SunChangzhe SunDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Changzhe Sun
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- María de Jesús Gálvez-VázquezMaría de Jesús Gálvez-VázquezDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by María de Jesús Gálvez-Vázquez
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- Ulrich MüllerUlrich MüllerSurface Science and Coating Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf 8600, SwitzerlandMore by Ulrich Müller
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- Rolf ErniRolf ErniElectron Microscopy Center, Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, Dübendorf 8600, SwitzerlandMore by Rolf Erni
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- Vitali GrozovskiVitali GrozovskiDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Vitali Grozovski
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- Yuhui Hou*Yuhui Hou*E-mail: [email protected]Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Yuhui Hou
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- Peter Broekmann*Peter Broekmann*E-mail: [email protected]Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, Bern 3012, SwitzerlandMore by Peter Broekmann
Abstract
Colloidal electrocatalysts are commonly synthesized using organic capping agents (surfactants), which control the size distribution and shape of the resulting nano-objects and prevent them from agglomerating during and after synthesis. However, the presence of a surfactant shell on the catalyst is detrimental, as the resulting performance of the electrocatalyst depends crucially on the ability of reactants to access active surface sites. Techniques for postsynthesis deprotection are therefore mandatory for removing the capping agents from the otherwise blocked reactions sites without compromising the structural integrity of the nanocatalysts. Herein, we present silver nanowires (Ag-NWs)—produced via PVP-assisted polyol synthesis (PVP, polyvinylpyrrolidone)—as effective catalysts for the electrochemical CO2 reduction reaction (ec-CO2RR), which reach Faradaic efficiencies close to 100% for CO formation after deprotection by a so-called “electrochemical looping” (ec-l) pretreatment. Electrochemical looping refers to a sequence of potentiostatic CO2 electrolysis experiments that exhibit well-defined starting (Estart), vertex (Evertex), and end (Eend) potentials. The resulting product distribution undergoes a profound hysteresis in the forward and corresponding backward run of the electrochemical looping experiment, thus pointing to an effective deprotection of the catalyst as made evident by postelectrolysis XPS inspection. These results can be considered as a prime example demonstrating the importance of the catalyst’s “history” for the resulting ec-CO2RR performance. These transient (non-steady-state) effects are crucial in particular for the initial stage of the CO2 electrolysis reaction and for catalyst screening approaches carried out on the time scale of hours.
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