Bi-defect sites are highly effective for CO2 reduction (CO2RR) to formic acid, yet most catalytic surfaces predominantly feature inert, non-defective Bi sites. To overcome this limitation, herein, tensile strain is introduced on wholescale non-defective Bi sites. Under rapid thermal shock, the Bi-based metal-organic framework (Bi-MOF-TS) shows weakened Bi-O bonds and produced tiny Bi clusters. During electrochemical reduction, these clusters create numerous continuous vacancies, inducing weak tensile strain over a large range of surrounding non-defective Bi sites. This strain enhances *OHCO intermediates adsorption and substantially lowers the reaction barrier. As a result, Bi-MOF-TS achieves a faradaic efficiency above 90% across 800 mV potential range, with an impressive formate partial current density of -995 ± 93 mA cm-2. Notably, Bi-MOF-TS exhibits a high HCOOH faradaic efficiency of 96 ± 0.64% at 400 mA cm-2 in acidic electrolyte and a high single-pass carbon conversion efficiency (SPCE) of 62.0%. Additionally, a Zn-CO2 battery with Bi-MOF-TS as the cathode demonstrates a peak power density of 21.4 mW cm-2 and maintains stability over 300 cycles.

Nanotechnology Centre Centre for Energy and Environmental Technologies VŠB─Technical University of Ostrava Ostrava Poruba Czech Republic

School of Chemical Sciences University of Auckland Auckland New Zealand

School of Materials and Energy University of Electronic Science and Technology of China Chengdu PR China

School of the Environment and Safety Engineering Jiangsu University Zhenjiang PR China

SEU FEI Nano Pico Center Key Laboratory of MEMS of the Ministry of Education The Southeast University Nanjing 210096 PR China

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of Technology Wuhan Hubei PR China

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Activating inert non-defect sites in Bi catalysts using tensile strain engineering for highly active CO2 electroreduction