Heterogeneous Hollow Multi‐Shelled Structures with Amorphous‐Crystalline Outer‐Shells for Sequential Photoreduction of CO₂

Abstract

Constructing delicate nano‐/microreactors with tandem active sites in hierarchical architectures is a promising strategy for designing photocatalysts to realize the challenging but attractive CO2 reduction. Herein, hollow multi‐shelled structure (HoMS) based microreactors with spatial ordered hetero‐shells are fabricated, which achieve two‐step CO2‐to‐CH4 photoreduction. The multiple inner CeO2 shells increase the number of active catalytic sites to ensure efficient first‐step reaction for generating CO, along with enriching the local CO concentration. The second‐step CO‐to‐CH4 reaction is consequently induced by amorphous TiO2 (A‐TiO2) composites on the adjacent outer‐most shell, thus realizing the CO2‐to‐CH4 conversion capability using one CeO2@CeO2/A‐TiO2 HoMS. In‐depth explorations in the microreactors provide compositional, structural, and interfacial guidance for engineering HoMS‐based microreactors with temporally–spatially ordered shells toward efficient tandem catalysis.

Construction of a Cu@hollow TS‐1 nanoreactor based on a hierarchical full‐spectrum solar light utilization strategy for photothermal synergistic artificial photosynthesis

“…These results indicate that the nanoreactors preferentially promote the adsorption of CO 2 molecules as well as the intermediates, therefore promoting both STY and C−C coupling probability, which is consistent with findings in the literature. 41,42 The size of cavities was also regulated by changing the etching time (Figure S3), and their influences on activities were investigated, as shown in Figure S12. The results demonstrate that larger cavities are beneficial to activity, while excessive etching time would lead to a decrease in activities.…”

Steering CO2electroreduction selectivity towards CH4and C2H4on a tannic acid-modified Cu electrode

“…are more desired with higher economic value since hydrocarbons such as CH 4 and C 2 H 4 are attractive due to their easy transport, convenient storage and high energy value. 13 However, it is difficult to tailor the selectivity of hydrocarbons because of multiple reaction pathways and the competing hydrogen evolution reaction (HER) in the CO 2 RR. In the process of the CO 2 RR on Cu catalysts, there are two significant factors having crucial effects on the selectivity of hydrocarbons.…”

A layer by layer strategy for the TiO2/CuxO/CeO2hierarchical structure supported on carbon cloth as a photocarrier-assisted photothermal catalyst with fast visible light response

“…Solar driven catalysis has received much attention in recent years, and can directly utilize sunlight especially in the visible and near-infrared bands as the energy source. 1,2 Materials with a strong light-to-heat response showing good photothermal (PT) effects have been widely used for cancer treatment, 3,4 water separation and desalination, [5][6][7][8] CO 2 reduction to prepare high-value fuels and chemical products, [9][10][11][12][13] and environmental pollutant purification. 14 In general, black or colored ones, such as defect-rich nanostructures, narrow-band-gap semiconductors, and noble metals, are all good candidates for PT catalysis.…”