Adaptive lattice-matched MOF and COF core-shell heterostructure for carbon dioxide photoreduction

Rational design of photocatalysts is critical for efficient solar-light driven carbon dioxide reduction. The conjugation of metal-organic framework (MOF) and covalent organic framework (COF) is a promising strategy but limited by the disparate interfacial energy and nucleation kinetics between heteroid MOF and COF. Herein, a lattice-matched MOF@COF core-shell catalyst, i.e., UiO-MOF@TpPaCOF, is developed via an in situ epitaxial growth strategy. The coherent interface of (111)UiO-66-NH2//(001)TpPa-COF meets both kinetic and thermodynamic driving force requirements. Moreover, the free rotation of linkers exhibits dynamic self-adaptive behavior to lower the lattice misfit. In solar-light-driven carbon dioxide reduction, the UiO-MOF@TpPa-COF could induce the electron migration from TpPa-COF to UiO-66-NH2 by directional charge transfer channels. As a result, the UiO-MOF@TpPa-COF achieves nearly 100% selectivity for the carbon dioxide photoreduction to formic acid, with a high rate of 178.3 mmol g -1$h-1. This contribution demonstrates that the design of lattice-matched MOF@COF catalysts could be a paradigm for carbon dioxide photoconversion.