A Strain-Engineered 0D/1D Heterojunction of InVO4/Cu-TbFeO3 for High- Selectivity CO2 Photoreduction

TL;DR

This paper reports a novel 0D/1D heterojunction catalyst that enhances CO2 photoreduction efficiency and selectivity through defect engineering, strain management, and interfacial design, achieving high CO yield and stability.

Contribution

It introduces a multi-synergetic 0D/1D heterojunction with defect and strain engineering to significantly improve CO2 photoreduction performance.

Findings

Enhanced CO yield of 65.75 mmole g-1.h-1

High selectivity of 95.93% for CO production

Extended charge carrier lifetime of 64.70 ns

Abstract

The catalytic CO2 photoreduction to CO is significantly hindered by the pervasive kinetic bottleneck of *CO-desorption and inefficient charge separation. Surpassing the conventional single photocatalytic strategy, herein, a multi-synergetic 0D/1D S-scheme heterojunction by precisely assembling 0D InVO4 nanoparticles on 1D Cu-doped TbFeO3 (IVO/CTFO). This nano-heterojunction is rationally designed at multiple steps where Cu2+ substitution at the Fe3+ site induces a compression in lattice strain and oxygen vacancies (VO), acting as electron traps and CO2 chemisorption sites, which breaks spin-polarization of pristine TbFeO3 to facilitate multichannel charge flow. The 0D/1D strategy couples the maximum surface active-sites and short charge diffusion routes with directional charge migration. Moreover, a 0D/1D lattice mismatch creates a built-in electric field at the interface, resulting in an enhanced lifetime (64.70 ns) of charged species, an efficient CO yield (65.75 mmole g-1.h-1), and high selectivity (95.93%). DFT calculations and experimental findings confirmed the Fermi level shift toward the conduction band and the existence of spin-hybridization. Operando-DRIFTS and the free-energy diagram unveil a H+ mediated mechanism at the interface, alongside a reduction in energy barrier for CO2 photoreduction from *COOH to *CO. Thus, this study presents an excellent approach that integrates defect-engineering, strain-compression, and interfacial design in advancing solar fuels production.