# Near-unity CO2-to-ethylene photoconversion over low coordination single-atom catalysts

## TL;DR

A new catalyst efficiently converts CO2 into ethylene using atomic-level coordination engineering, achieving near-complete selectivity.

## Contribution

A low-coordination manganese single-atom catalyst is developed for high-efficiency CO2-to-ethylene conversion.

## Key findings

- Manganese single-atom catalyst in zinc sulfide achieves 99.1% ethylene selectivity.
- Sulfur vacancies at coordination sites enhance CO adsorption and C–C coupling efficiency.

## Abstract

Photocatalytic conversion of carbon dioxide to value-added chemicals, particularly multi-carbon products, offers a promising route toward carbon-neutral cycles. However, achieving high activity and selectivity remains extremely challenging due to the instability of key reaction intermediates and limited C–C coupling efficiency. Herein, we report a low-coordination manganese single-atom catalyst embedded in zinc sulfide (Mn1–ZnSv) that enables efficient and selective CO2-to-C2+ conversion. In-situ spectroscopic analyses and density functional theory calculations reveal that sulfur vacancies are created at the Mn single-atom coordination sites and induce the formation of coordination-unsaturated Mn-S2 configuration. The asymmetric coordination environment of Mn modulates local charge distribution, strengthens *CO adsorption, and promotes *CO and *CHO coupling to form the *COCHO intermediate for efficient C–C coupling. As a result, the Mn1–ZnSv catalyst achieved 99.1% selectivity for ethylene with a formation rate of 76.6 μmol g-1 h-1. This study highlights the critical role of atomic-level coordination engineering in advancing photocatalytic CO2-to-C2+ conversion.

This work develops an atomic-level coordination engineering strategy that strengthens key intermediate adsorption to promote C–C coupling, enabling highly selective photocatalytic CO2 conversion to ethylene.