Selective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation

Abstract

Abstract The efficient use of renewable X/γ-rays or accelerated electrons for chemical transformation of CO 2 and water to fuels holds promise for a carbon-neutral economy; however, such processes are challenging to implement and require the assistance of catalysts capable of sensitizing secondary electron scattering and providing active metal sites to bind intermediates. Here we show atomic Cu-Ni dual-metal sites embedded in a metal-organic framework enable efficient and selective CH 3 OH production (~98%) over multiple irradiated cycles. The usage of practical electron-beam irradiation (200 keV; 40 kGy min −1 ) with a cost-effective hydroxyl radical scavenger promotes CH 3 OH production rate to 0.27 mmol g −1 min −1 . Moreover, time-resolved experiments with calculations reveal the direct generation of CO 2 •‒ radical anions via aqueous electrons attachment occurred on nanosecond timescale, and cascade hydrogenation steps. Our study highlights a radiolytic route to produce CH 3 OH with CO 2 feedstock and introduces a desirable atomic structure to improve performance.