Asymmetric Coupled Dual‐Atom Sites for Selective Photoreduction of Carbon Dioxide to Acetic Acid

Abstract

Photocatalytic reduction of CO 2 to value-added liquid fuels is a promising approach to alleviate the global energy and environmental problems. However, highly selective production of C2+ products from CO 2 reduction reaction (CO 2 RR) is very difficult because of the sluggish CC coupling reaction. An asymmetric coupled heteronuclear photocatalyst is designed to overcome this limitation. The new catalyst contains single atoms of nickel and cobalt loaded on titanium dioxide. It exhibits an impressive 71% selectivity for acetic acid. The experimental data and theoretical calculations reveal that the Ni and Co single atom sites not only significantly lower the energy barrier of electron transfer in photocatalysis but also efficiently promote the CC coupling toward CH 3 COOH. The high activity of such a heteronuclear catalyst system will shed light on the future development of effective materials for CO 2 RR.

Enabling Efficient Photocatalytic Hydrogen Evolution via In Situ Loading of Ni Single Atomic Sites on Red Phosphorus Quantum Dots

“…[ 45–48 ] Furthermore, the EXAFS wavelet transforms (WT) analysis of Ni K‐edge EXAFS oscillations was displayed to distinguish between backscattered atoms and achieve strong resolution in k and R spaces. [ 49,50 ] The results show the intensity maximum (12.1 Å −1 ) attributed to the Ni‐P bond and the absence of the Ni‐Ni contribution (8.2 Å −1 ). This further proves that Ni atoms are atomically dispersed on the RPQD substrate with a coordination environment consisting of O and P. [ 51 ] Furthermore, Fourier transform infrared (FTIR) was also used to confirm the existence of Ni‐P moiety (Figures S12 and S13, Supporting Information).…”

Dinuclear metal synergistic catalysis for energy conversion

“…Many strategies have also been developed to design and synthesize heterogeneous DMCs to achieve photo- and electrocatalytic CO 2 RR. 221–276 However, more examples have been reported for the latter.…”

“…Consequently, NiCo–TiO 2 displayed an impressive catalytic performance with CH 3 COOH production rate of 22.6 μmol g −1 h −1 and selectivity of 71%. 226…”

Recent Progress of Diatomic Catalysts: General Design Fundamentals and Diversified Catalytic Applications

“…An asymmetric coupled heteronuclear photocatalyst (Ni and Co single atom sites) loaded on titanium dioxide also exhibited an impressive 71% selectivity for acetic acid in CO 2 RR (CC coupling toward CH 3 COOH). [ 198 ] 2) Photocatalytic oxidation reaction: the construction of CuN 4 and CSC diatomic sites can be used as electron receptors and electron donors, respectively, to improve the separation efficiency of photogenerated carriers for photocatalytic oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐dimethylfuran (DFF). The photogenerated electrons are easily captured at the CuN 4 site and transferred to the oxygen molecule to generate superoxide radical (•O 2− ), while the hole (H + ) is limited to the S atom for direct oxidation.…”