Mechanistic exploration in controlling the product selectivity via metals in TiO2 for photocatalytic carbon dioxide reduction

Singh, Shreya; Kumar, Raushan; Pant, Kamal K.; Kumar, Sushant; Joshi, Dhavalkumar; Biswas, Pratim

doi:10.1016/j.apcatb.2024.124054

Cited by 4 publications

(2 citation statements)

References 51 publications

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Section: Introductionmentioning

confidence: 99%

“…Elemental doping is regarded as an effective strategy for modulating the physicochemical properties and electronic structure of photocatalysts, therefore optimizing the light absorption and charge separation capabilities. , Moreover, the doped ions can possibly act as the active sites for the photocatalytic reaction, thus enhancing the catalytic activities. , Among the doping ions, Cu ions have received an increasing amount of attention owing to the easy formation of oxygen vacancy active sites and favorable adsorption properties with respect to C-containing intermediates of Cu-related species. , For example, Li and co-workers recently have developed a Cu/Cu + @TiO 2 photocatalyst prepared via an in situ ionothermal method and demonstrated that the Cu + -O valences formed inside the lattice of TiO 2 can enhance the carrier transport efficiency and metal Cu on the TiO 2 surface acts as the active sites for CO 2 reduction . Notably, Wang et al constructed a Cu δ+ -doped CeO 2 –TiO 2 photocatalyst for CO 2 reduction via the pyrolytic transformation of a Cu 2+ -Ce 3+ /MIL-125-NH 2 precursor, and the photocatalyst exhibited a C 2 H 4 production rate of 4.51 μmol –1 (g of catalyst) −1 h –1 and 73.9% selectivity in terms of electron utilization .…”

Section: Introductionmentioning

confidence: 99%

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Shaping and Doping Metal–Organic Framework-Derived TiO₂ to Steer the Selectivity of Photocatalytic CO₂ Reduction toward CH₄

Li,

Zhou

et al. 2024

Inorg. Chem.

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Steering selectivity in photocatalytic conversion of CO 2 , especially toward deep reduction products, is vital to energy and environmental goals yet remains a great challenge. In this work, we demonstrate a facet-dependent photocatalytic selective reduction of CO 2 to CH 4 in Cudoped TiO 2 catalysts exposed with different facets synthesized by a topological transformation from MIL-125 (Ti) precursors. The optimized round cake-like Cu/TiO 2 photocatalyst mainly exposed with the (001) facet exhibited a high photocatalytic CO 2 reduction performance with a CH 4 yield of 40.36 μmol g −1 h −1 with a selectivity of 94.1%, which are significantly higher than those of TiO 2 (001) (4.70 μmol g −1 h −1 and 52.6%, respectively), Cu/TiO 2 (001 + 101) (18.95 μmol g −1 h −1 and 69.6%, respectively), and Cu/TiO 2 (101) (14.73 μmol g −1 h −1 and 78.9%, respectively). The results of experimental and theoretical calculations demonstrate that the Cu doping dominating the promoted separation and migration efficiencies of photogenerated charges and the preferential adsorption on (001) facets synergistically contribute to the selective reduction of CO 2 to CH 4 . This work highlights the significance of synergy between facet engineering and ion doping in the design of high-performance photocatalysts with respect to selective reduction of CO 2 to multielectron products.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Shaping and Doping Metal–Organic Framework-Derived TiO₂ to Steer the Selectivity of Photocatalytic CO₂ Reduction toward CH₄

Li,

Zhou

et al. 2024

Inorg. Chem.

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Exploring the Feasibility of Copper Incorporation in Halide Perovskites: Impact on CO₂ Photoreduction Performance

Tailor,

Singh,

Singh

et al. 2024

Advanced Energy Materials

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Double perovskite have attracted substantial attention as prospective materials for applications in optoelectronics and photocatalysis. Significant efforts are devoted to modulating the properties of double perovskites to improve their performance. One promising approach involves substituting silver (Ag) with copper (Cu), which offers favorable electronic characteristics. Despite promising theoretical predictions, the experimental synthesis of copper‐based double perovskites has presented notable challenges. Here, the challenges of Cu incorporation in double perovskites and the subsequent – impact of Cu on the photocatalytic activity of halide perovskites toward CO2 reduction are explored. Combining detailed computational thermodynamic studies, it is found that Cu does not form the traditional double perovskite structure that is Cs2CuBiCl6; it stays as an interstitial dopant in its pristine Cs3Bi2Cl9 structure. The Cu‐Cs3Bi2Cl9 are found to exhibit enhanced CO2 photoreduction activity than the pristine Cs3Bi2Cl9. Further, transient absorption results show that Cu dopants enhance the carrier generation because of introduced sub‐bandgap states, and it is found that carrier decay lifetime is elevated in Cu‐Cs3Bi2Cl9, which can enhance the participation of carriers in CO2 photoreduction. The study explores the challenges and opportunities of copper doping in halide perovskites, offering the potential for developing efficient CO2 reduction photocatalysts.

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Modulation of Selectivity and Activity of Ni/TiO₂ Catalysts by Metal Dispersion in Photothermal CO₂ Hydrogenation

Alfonso‐González,

Iglesias‐Juez,

Fresno

et al. 2024

ChemCatChem

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Ni/TiO2 catalysts are efficient and cost‐effective for photothermal CO2 hydrogenation. However, the achieved CO/CH4 ratio strongly depends on the specific characteristics of these catalysts. To further ascertain the role of metal dispersion and photoactivation on selectivity, in this work we investigate the impact of Ni loading over high surface area anatase on the photothermal performance. Catalysts with 3 and 10 wt. % of Ni prepared by incipient wetness impregnation show initial good dispersion of the metal, although after activation in H2 metallic Ni nanoparticles are observed for 10%Ni/TiO2. This last catalyst demonstrates superior CO2 hydrogenation activity at high temperature, but below 200 ºC it is overpassed by the catalyst with 3 wt % Ni/TiO2. The selectivity varies remarkably with Ni loadings. Thus, at 350 °C about 93 % of methane is obtained over 10 wt.% Ni/TiO2, while 3%Ni/TiO2 yields about 97 % of CO. Low‐intensity UV irradiation enhances performance, particularly at temperatures below 200 ºC, where an increment in the production of methane of up to 75 % is observed for 3 wt.% Ni/TiO2 at 200 ºC. These results highlight the influence of metal dispersion, along with irradiation on modulating the selectivity of the photothermal CO2 hydrogenation

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Mechanistic exploration in controlling the product selectivity via metals in TiO2 for photocatalytic carbon dioxide reduction

Cited by 4 publications

References 51 publications

Shaping and Doping Metal–Organic Framework-Derived TiO₂ to Steer the Selectivity of Photocatalytic CO₂ Reduction toward CH₄

Shaping and Doping Metal–Organic Framework-Derived TiO₂ to Steer the Selectivity of Photocatalytic CO₂ Reduction toward CH₄

Exploring the Feasibility of Copper Incorporation in Halide Perovskites: Impact on CO₂ Photoreduction Performance

Modulation of Selectivity and Activity of Ni/TiO₂ Catalysts by Metal Dispersion in Photothermal CO₂ Hydrogenation

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Mechanistic exploration in controlling the product selectivity via metals in TiO2 for photocatalytic carbon dioxide reduction

Cited by 4 publications

References 51 publications

Shaping and Doping Metal–Organic Framework-Derived TiO2 to Steer the Selectivity of Photocatalytic CO2 Reduction toward CH4

Shaping and Doping Metal–Organic Framework-Derived TiO2 to Steer the Selectivity of Photocatalytic CO2 Reduction toward CH4

Exploring the Feasibility of Copper Incorporation in Halide Perovskites: Impact on CO2 Photoreduction Performance

Modulation of Selectivity and Activity of Ni/TiO2 Catalysts by Metal Dispersion in Photothermal CO2 Hydrogenation

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Shaping and Doping Metal–Organic Framework-Derived TiO₂ to Steer the Selectivity of Photocatalytic CO₂ Reduction toward CH₄

Shaping and Doping Metal–Organic Framework-Derived TiO₂ to Steer the Selectivity of Photocatalytic CO₂ Reduction toward CH₄

Exploring the Feasibility of Copper Incorporation in Halide Perovskites: Impact on CO₂ Photoreduction Performance

Modulation of Selectivity and Activity of Ni/TiO₂ Catalysts by Metal Dispersion in Photothermal CO₂ Hydrogenation