Tailoring the d-Band Center of Double-Perovskite LaCo_{x}Ni_{1–x}O₃ Nanorods for High Activity in Artificial N₂ Fixation

Kaibin Chu; Michiel De Ras; Dewei Rao; Johan A. Martens; Johan Hofkens; Feili Lai; Tianxi Liu

doi:10.1021/acsami.1c01510

journal article·2021-03-24Open access

Tailoring the d-Band Center of Double-Perovskite LaCo_xNi_1–xO₃ Nanorods for High Activity in Artificial N₂ Fixation

Kaibin Chu, Michiel De Ras, Dewei Rao, Johan A. Martens, Johan Hofkens, Feili Lai, Tianxi Liu

ACS Applied Materials & Interfaces· Volume 13· Issue 11

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Source abstract

Abstract

The d-band center of a catalyst can be applied for the prediction of its catalytic activity, but the application of d-band theory for the electrocatalytic nitrogen reduction reaction (eNRR) has rarely been studied in perovskite materials. In this work, a series of double-perovskite LaCoxNi1–xO3 (LCNO) nanorods (NRs) were synthesized as models, where the d-band centers can be modulated by changing the stoichiometric ratios between Co and Ni elements. Experimentally, the LCNO-III NRs (x = 0.5) attained the highest faradic efficiency and NH3 yield rate among various LCNO NRs. This result matches well with the finding from theoretical calculations that LCNO-III has the most positive d-band center (εd = −0.96 eV vs Fermi level), thus confirming that LCNO-III shows the strongest adsorption ability for N2 molecules (adsorption energy value of −2.01 eV) for the subsequent N2 activation and reduction reactions. Therefore, this work proposes a general rule to adopt for developing novel catalysts (especially perovskite-based catalysts) for substantially increasing the eNRR activity by modulating the corresponding d-band centers.

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Research context

Nanomaterials Electronic materials Catalysis & surfaces

OpenAlex topics: Ammonia Synthesis and Nitrogen Reduction · Advanced Photocatalysis Techniques · Catalytic Processes in Materials Science

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, International Joint Research Laboratory for Nano Energy Composites, Jiangnan University, Wuxi 214122, P. R. China

Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven 3001, Belgium

School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, P. R. China

Centre of Surface Chemistry and Catalysis: Characterisation and Application Team, KU Leuven, Leuven 3001, Belgium

Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz 55128, Germany

Funding

National Natural Science Foundation of China · Interne Fondsen KU Leuven · Program of the Shanghai Academic Research Leader · Moonshot cSBO project P2C · Shanghai Scientific and Technological Innovation Project · Jiangsu Overseas Visiting Scholar Program for University Prominent Young and Mid-aged Teachers and President

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