Regulating Photocatalytic CO₂ Reduction Kinetics through Modification of Surface Coordination Sphere

Abstract

Solar‐driven reduction of CO2 to value‐added products represents a sustainable strategy for mitigating the greenhouse effect and addressing the related green‐energy crisis. Herein, it is demonstrated that modifying the surface coordination sphere can significantly enhance the reaction kinetics and overall efficiency of CO2 reduction. More specifically, the decoration of isolated Mn atoms over the multi‐edged TiO2 nano‐pompons (Mn/TONP) upshifts the d‐band center that allows favorable CO2 adsorption. Ultrafast spectroscopy demonstrates the greatly accelerated charge transfer between photoexcited multi‐edged TONP and the newly implanted Mn reactive centers, supplying long‐lifetime electrons to reduce absorbed CO2 molecules. By integrating adsorption and activation functions into the newly decorated Mn sites, the developed photocatalyst demonstrate impressive capacity for CO2 reduction (80.51 mmol g−1 h−1). The surface modulation strategy at the atomic level not only opens new avenues for regulating the reaction kinetics toward photocatalytic CO2 reduction, but also paves the way for the rational design of highly efficient and selective photocatalysts for clean energy conversion.

Photocatalytic reduction of Cr(vi) on a series of defective MnmIn2S3+m (m = 1–5, integer)

“…To reveal the photocatalytic mechanism of the high Cr( vi ) reduction rate promoted by defective Mn m In 2 S 3+ m , a variety of characterization tests were carried out. 37–39 As is known, many factors affect the performance of photocatalysts, such as optical properties and the separation and migration of the photo-excited carriers. Fig.…”

Low Content Ga2O3 Enables the Direct Methane Conversion

“…After collecting the background, CH 4 was introduced to the cell to allow the adsorption for 30 min, and then N 2 was flushed to remove the gaseous CH 4 in the cell and the physically adsorbed CH 4 on the surface of the sample for 15 min. Finally, the temperature was increased the target temperature, and the spectra were recorded by collecting 8 scans with a resolution of 4 cm –1 . Thermogravimetry analysis was conducted on a TGA4000 (PerkinElmer) in air at the temperature range from 30 to 800 °C with a heating rate of 10 °C/min.…”

Metal-Based Ionic Liquid Induced Strategy for Loading Single Atoms and the Coordination Mode Effect on CO2 Photoreduction

“…The monodentate carbonate (m-CO 3 2– ) and bicarbonate (HCO 3 – ) are detected at 1478 and 1397 cm –1 . After xenon lamp irradiation, the new peaks present at 1560 and 1570 cm –1 are related to *COOH, an important intermediate in the photocatalytic reduction of CO 2 . , The spectrogram characteristics of Bi 24 O 31 Br 10 and Co sur -Bi 24 O 31 Br 10 -0.05 are identical, indicating that the adsorption and activation pathways of the CO 2 molecules remain similar. According to the above analyses and DFT calculations (Figure ), the possible CO 2 photoreduction mechanism for producing CO is described as follows: CO 2 molecules are adsorbed on the catalysts’ surface and H 2 O molecules are dissociated to form H + and OH – .…”