Tuning W₁₈O₄₉/Cu₂O{111} Interfaces for the Highly Selective CO₂ Photocatalytic Conversion to CH₄

Abstract

As a multiple proton-coupled electron transfer process, photocatalytic conversion of CO2 usually produces a wide variety of products. Improving the yield and selectivity of CO2 to the single product is still a significant challenge. In this work, we describe that the rationally constructed W18O49/Cu2O­{111} interfaces achieve highly selective CO2 photocatalytic conversion to CH4. In situ Fourier transform infrared spectroscopy measurements reveal that the formation of W18O49/Cu2O­{111} interfaces restrains the desorption of CO* intermediates in CO2 photocatalytic conversion. UPS spectra, PL spectra, and photocurrent curves show that more photogenerated electrons are excited and transferred to W18O49/Cu2O­{111} interfaces. All of these play critical roles in CH4 production. As an outcome, the yield rate of CO2 photocatalytic conversion to CH4 was enhanced from 6.5 to 17.20 μmol g–1 h–1 with selectivity as high as 94.7%. The work demonstrates the feasibility and versatility of interface engineering in achieving highly selective CO2 photocatalytic conversion.

Integrated S‐Scheme Heterojunction of Amine‐Functionalized 1D CdSe Nanorods Anchoring on Ultrathin 2D SnNb2O6 Nanosheets for Robust Solar‐Driven CO2 Conversion

“…[5][6][7][8][9][10][11] However, the low CO 2 conversion efficiency and poor stability of these photocatalysts still restricts their practical implementation, which could be attributed to high CO 2 activation energy barriers, rapid recombination of charge carriers, and sluggish kinetics of multiple electron transfer. [12][13][14][15][16][17] Thus, designing a novel photocatalyst and/or system with highly efficient CO 2 conversion to address the aforementioned issues remains urgently desirable.…”

“…[5][6][7][8][9][10][11] However, the low CO 2 conversion efficiency and poor stability of these photocatalysts still restricts their practical implementation, which could be attributed to high CO 2 activation energy barriers, rapid recombination of charge carriers, and sluggish kinetics of multiple electron transfer. [12][13][14][15][16][17] Thus, designing a novel photocatalyst and/or system with highly efficient CO 2 conversion to address the aforementioned issues remains urgently desirable.Among various strategies, constructing heterostructures is an intriguing method for boosting CO 2 photoreduction performance by raising the utilization of visible light and suppressing the reunion of charge carriers. [18] Z-scheme and S-scheme heterostructures with high redox capacity have been widely studied.…”

Well-defined Cu2O photocatalysts for solar fuels and chemicals

“…Another possible way to increase the photoreduction performance of cuprous oxide is the suitable formation of Z scheme-based hybrids by coupling the p-type Cu 2 O semiconductor with n-type wide bandgap semiconductors such as TiO 2 , ZnO and W 18 O 49 . 210,211,[219][220][221][222] Precise control of the morphology and size can efficiently increase the photoreduction rate and product selectivity. A Z-scheme heterojunction can limit the issue of recombination of the charge carriers, improving the stability of the photocatalyst.…”

Engineering approach toward catalyst design for solar photocatalytic CO 2 reduction: A critical review

“…As shown in Figure 1, various products can be yielded through different reaction routes and mechanisms of CO 2 reduction, which greatly depend upon the reaction conditions and the utilized photocatalysts. Currently, the most common products obtained from artificial photosynthesis are CO, CH 4 , and CH 3 OH while few works related to C 2+ products, such as ethanol (CH 3 CH 2 OH) and ethylene (C 2 H 4 ) are reported 25,39,84,85 . Furthermore, the reaction of photocatalytic CO 2 reduction can be proceeded both in liquid and gas phase medium.…”

“…In contrast, converting CO 2 into highly value‐added chemical fuels makes more sense. Thus, scientists have transferred their research focus to artificial conversion of CO 2 and developed some major strategies, including conventional thermochemical, 14‐19 electrochemical, 20‐24 and photocatalytic methods 25‐34 . In the last decade, thermochemical conversion of CO 2 has witnessed a significant progress in both product selectivity and productivity (turnover numbers, TONs).…”