Electrochemical reduction of carbon dioxide (ERCO2 ) is an attractive and sustainable approach to close the carbon loop. Formic acid is a high-value and readily collectible liquid product. However, the current reaction selectivity remains unsatisfactory. In this study, the bismuth-containing metal-organic framework CAU-17, with morphological variants of hexagonal prisms (CAU-17-hp) and nanofibers (CAU-17-fiber), is prepared at room temperature through a wet-chemical approach and employed as the electrocatalyst for highly selective CO2 -to-formate conversion. An H3 BTC-mediated morphology reconstruction is systematically investigated and further used to build a CAU-17-fiber hierarchical structure. The as-prepared CAU-17-fiber_400 electrodes give the best electrocatalytic performance in selective and efficient formate production with FEHCOO- of 96.4 % and jCOOH- of 20.4 mA cm-2 at -0.9 VRHE . This work provides a new mild approach for synthesis and morphology engineering of CAU-17 and demonstrates the efficacy of morphology engineering in regulating the accessible surface area and promoting the activity of MOF-based materials for ERCO2 .

Center for Advanced Functional Nanorobots Department of Inorganic Chemistry Faculty of Chemical Technology University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Central Laboratories University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Department of Chemical and Biomolecular Engineering Yonsei University 50 Yonsei ro Seodaemun gu 03722 Seoul Korea

Department of Medical Research China Medical University Hospital China Medical University No 91 Hsueh Shih Road 40202 Taichung Taiwan P R China

Future Energy and Innovation Laboratory Central European Institute of Technology Brno University of Technology Purkyňova 656 123 CZ 616 00 Brno Czech Republic

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