Light-switchable catalytic activity of Cu for oxygen reduction reaction
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Light-switchable catalytic activity of Cu for oxygen reduction reaction Yue ZHANG1, Yihong YU1, Xiankai FU1, Zhisen LIU2, Yinglei LIU1, and Song LI (✉)1,3 1 Key Lab for Anisotropy and Texture of Materials (MOE), School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China 2 Liaoning Academy of Analytical Sciences, Shenyang 110015, China 3 Research Center for Metallic Wires, Northeastern University, Shenyang 110819, China
© Higher Education Press 2020
ABSTRACT: The surface reactivity of metals is fundamentally dependent on the local electronic structure generally tailored by atomic compositions and configurations during the synthesis. Herein, we demonstrate that Cu, which is inert for oxygen reduction reaction (ORR) due to the fully occupied d-orbital, could be activated by applying a visible-light irradiation at ambient temperature. The ORR current is increased to 3.3 times higher in the potential range between -0.1 and 0.4 V under the light of 400 mW$cm-2, and the activity enhancement is proportional to the light intensity. Together with the help of the first-principle calculation, the remarkably enhanced electrocatalytic activity is expected to stem mainly from the decreased metal-adsorbate binding by photoexcitation. This finding provides an additional degree of freedom for controlling and manipulating the surface reactivity of metal catalysts besides materials strategy. KEYWORDS:
photochemistry; surface reactivity; oxygen adsorption; copper
Developing highly active electrocatalysts is crucial for energy conversion or chemicals production on demand in the sustainable approach [1–3]. The oxygen reduction reaction (ORR) as the complementary half-reaction plays a crucial role in a number of electrochemical energy conversing processes or devices such as fuel cells and metal–air batteries [4–6]. Meanwhile, the ORR is a fundamentally important model reaction for exploration of the dependence of catalytic activity on materials chemistry and structure. The sluggish kinetics and large overpotential of the ORR limit the energy efficiency of the process, and highly active catalysts are thus in great need [7]. By now, the reported highly active electrocatalysts are dominated by noble metals, especially for Pt containing Received June 11, 2020; accepted July 28, 2020 E-mail: [email protected]
materials with moderate adsorption strength of oxygen species [8–11]. However, the wide employment of Ptbased electrocatalysts is inhibited by its high cost and low abundance, as well as its poor tolerance of CO. Though significant efforts have been devoted to reduce the contents of noble metals by increasing the efficiency per atom, including alloying, size and shape control, atomic dispersing, and introducing strains [10–13], the problems still remain unresolved. As a result, the exploration of highly efficient ORR electrocatalysts based on non-noble and abundant metals is of importance. Local electronic structure plays a decisive role in determining the catalytic activity of the metal cat
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