Bismuth atom tailoring of indium oxide surface frustrated Lewis pairs boosts heterogeneous CO2 photocatalytic hydrogenation

Abstract

The surface frustrated Lewis pairs (SFLPs) on defect-laden metal oxides provide catalytic sites to activate H2 and CO2 molecules and enable efficient gas-phase CO2 photocatalysis. Lattice engineering of metal oxides provides a useful strategy to tailor the reactivity of SFLPs. Herein, a one-step solvothermal synthesis is developed that enables isomorphic replacement of Lewis acidic site In3+ ions in In2O3 by single-site Bi3+ ions, thereby enhancing the propensity to activate CO2 molecules. The so-formed BixIn2-xO3 materials prove to be three orders of magnitude more photoactive for the reverse water gas shift reaction than In2O3 itself, while also exhibiting notable photoactivity towards methanol production. The increased solar absorption efficiency and efficient charge-separation and transfer of BixIn2-xO3 also contribute to the improved photocatalytic performance. These traits exemplify the opportunities that exist for atom-scale engineering in heterogeneous CO2 photocatalysis, another step towards the vision of the solar CO2 refinery.

Creation of Mo active sites on indium oxide microrods for photocatalytic amino acid production

“…The peaks at approximately 451.04 and 443.45 eV in the high-resolution XPS In 3d spectrum of Mo-In 2 O 3 are attributed to the 3d 3/2 and 3d 5/2 electrons of In 3+ , respectively (Fig. 2b) [48]. This pair of peaks is shifted to lower binding energies for Mo-In 2 O 3 , indicating the increase in the electron density around In atoms.…”

Design of Frustrated Lewis Pair in Defective TiO2 for Photocatalytic Non-Oxidative Methane Coupling

“…Recently, solid frustrated Lewis pair (FLP) composed of long-distanced Lewis acid (LA) and Lewis base (LB) sites on the solid surface have proven e cient for H 2 , CO 2 and CO activation [9][10][11][12] . The existence of steric hindrance between LA and LB leads to the unremitting attraction between Lewis pairs rather than bonding with each other, which has been extensively studied on metal oxides with unsaturated metal centers and metal terminal hydroxyl groups mediated by oxygen vacancies, typically seen in defective CeO 2 and In 2 O 3−x (OH) y [13][14][15][16][17] . While the C-H activation of arenes and heteroarenes by FLP has been achieved, the activation of aliphatic Csp 3 -H bonds remains a challenge to be solved [18][19][20][21] .…”

Significantly Raised Visible‐Light Photocatalytic H2 Evolution on a 2D/2D ReS2/In2ZnS4 van der Waals Heterostructure

“…Photocatalytic water splitting converts abundant sunlight into storable/carbon‐free H 2 . [ 1–43 ] Thus, it has attracted significant research attention. Of particular importance is the rational design of highly‐efficient, stable and inexpensive photocatalysts.…”