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

Abstract

The efficient use of renewable X/γ-rays or accelerated electrons for chemical transformation of CO2 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 CH3OH 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 CH3OH production rate to 0.27 mmol g−1 min−1. Moreover, time-resolved experiments with calculations reveal the direct generation of CO2•‒ radical anions via aqueous electrons attachment occurred on nanosecond timescale, and cascade hydrogenation steps. Our study highlights a radiolytic route to produce CH3OH with CO2 feedstock and introduces a desirable atomic structure to improve performance.

Effect of Ni content on Cu–Mn/ZrO2 catalysts for methanol synthesis from CO2 hydrogenation

“…This might be attributed to weakened interactions between copper and nickel, i.e., the transfer of electrons from Ni to Cu decreased due to the aggregation of Ni particles. 34 The XPS spectra of Mn 2p are shown in Fig. 4a.…”

Application of MOF-derived materials as electrocatalysts for CO2 conversion

“…Cu-based materials were the most widely reported catalysts for the electrocatalytic CO 2 RR to these two products. [122][123][124][125] To optimize the selectivity, the spacing between adjacent Cu sites needs to be adjusted so that each active site is isolated and dispersed, thus reducing the possibility of C-C coupling. For example, the through-hole carbon nanofibers with well-dispersed Cu single atoms (Cu SAs/THCF) showed good electrocatalytic activity for the reduction of CO 2 to methanol.…”

Recent progress of heterogeneous catalysts for transfer hydrogenation under the background of carbon neutrality

“…The overuse of nonrenewable fossil resources such as coal, oil and natural gas greatly increases CO 2 emission and the accompanying greenhouse effect, and thus it is necessary to develop renewable resources and CO 2 capture and utilization technologies. 1–7 For this, many chemists and materials scientists focus on the development of new renewable resources (wind, light, electricity, etc. ) and new materials such as nanomaterials.…”

“…In particular, in the context of carbon neutrality, the highly efficient conversion of CO 2 to formic acid and methanol is regarded as one of the most promising CO 2 direct conversion technologies for industrialization, which is undergoing rapid development. 5,8–14 For example, Yang et al recently synthesized a layered {001}-oriented Bi oxyhalide ( i.e. BiOX, X = Cl, Br or I) electrocatalyst to produce formic acid from CO 2 in a flow cell.…”