Photoelectrochemical investigation of the role of surface-modified Yb species in the photocatalytic conversion of CO2 by H2O over Ga2O3 photocatalysts

Deuterium(D)‐labeled aromatics play an essential part in the Yield of fine chemicals. However, deuteration reactions are particularly dependent on the specific chemical environment of the metal to finish the oxidative addition and reductive elimination. Herein, a complex valence Pt/Ca12Al14Ox catalyst was successfully synthesized for the deuteration of toluene using inexpensive D2O. It exhibited high deuteration efficiency, achieving 96% deuteration in just 4 hours, 14% higher than the most commonly Pt/C catalyst. The catalyst can also be reactivated and recycled up to 16 times. Multiple characterization techniques were used to demonstrate the interaction between Pt and Ca12Al14Ox generates the co‐existence of Pt(δ+) and Pt(0). The synergy between Pt(δ+) and Pt(0) can promote the completion of oxidation and elimination reactions. Thus, the complex valence of Pt improves the processes required for H−D exchange and boosts the reaction rate and stability of the hydrogen isotope exchange system.

show abstract

“…250 °C) and Al 2 O 3 ‐supported PtO x (ca. 319 °C) [35] . indicating the presence of strong interactions Pt and Ca 12 Al 14 O x .…”

Section: Resultsmentioning

confidence: 99%

“…319 °C). [35] indicating the presence of strong interactions Pt and Ca 12 Al 14 O x . The reduction temperature of PtO x species consisting of Pt(δ +) is much higher due to the addition of Pt atoms in the support, which allows the PtO x species to be stably bound to Ca 12 Al 14 O x -600.…”

Section: Resultsmentioning

confidence: 99%

Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

et al. 2023

View full text Add to dashboard Cite

show abstract

“…[ 146–148 ] In addition, creating acid–base sites or vacancy and ionic modification on the surface are capable of promoting light absorption, charge separation, and CO 2 activation. [ 149–151 ] 4) Schottky junction and Z‐scheme junction are typical and efficient heterojunctions that can well engineer the interface structure. In Schottky junction, electrons move from semiconductor to metal to obstruct backflow, resulting in a high charge transfer efficiency.…”

Section: Overview Of Photocatalysts For Co2 Reductionmentioning

confidence: 99%

Inside‐and‐Out Semiconductor Engineering for CO₂ Photoreduction: From Recent Advances to New Trends

et al. 2020

View full text Add to dashboard Cite

Photocatalytic CO2 reduction attracts substantial interests for the production of chemical fuels via solar energy conversion, but the activity, stability, and selectivity of products were severely determined by the efficiencies of light harvesting, charge migration, and surface reactions. Structural engineering is a promising tactic to address the aforementioned crucial factors for boosting CO2 photoreduction. Herein, a timely and comprehensive review focusing on the recent advances in photocatalytic CO2 conversion based on the design strategies over nano‐/microstructure, crystalline and band structure, surface structure and interface structure is provided, which covers both the thermodynamic and kinetic challenges in CO2 photoreduction process. The key parameters essential for tailoring the size, morphology, porosity, bandgap, surface, or interfacial properties of photocatalysts are emphasized toward the efficient and selective conversion of CO2 into valuable chemicals. New trends and strategies in the structural design to meet the demands for prominent CO2 photoreduction activity are also introduced. It is expected to furnish a comprehensive guideline for inside‐and‐out design of state‐of‐the‐art photocatalysts with well‐defined structures for CO2 conversion.

show abstract

“…Gallium oxide (Ga 2 O 3 ), a wide-band-gap semiconductor with large band-gap energy of 4.4–4.9 eV, has high voltage stability and exciton binding energy, making it famous for applications in electronic and optoelectronic devices. − Lately, Ga 2 O 3 as a photocatalyst has been applied in photocatalytic environment purification and energy conversion, such as overall water-splitting, − organics degradation, − and CO 2 reduction. − Ga 2 O 3 possesses appropriate valence and conduction band edge with satisfied redox potential for most reactions. It can generate photoexcited electrons with large mobility due to the conduction band formed by hybridized sp orbitals with a large dispersion.…”

Section: Introductionmentioning

confidence: 99%

Crystal-Structure-Dependent Photocatalytic Redox Activity and Reaction Pathways over Ga₂O₃ Polymorphs

Chen

Lei

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Differentiated crystal structures generally affect the surface physicochemical properties of catalysts, causing variety in catalytic activity between polymorphs. However, the underlying mechanism has not been completely revealed, especially the influence of surface physicochemical properties on photocatalytic redox activity and the reaction mechanism. In this work, we reveal the mechanism of surface redox properties on different crystal forms of gallium oxide from a molecular level. α-Ga2O3 and β-Ga2O3 exhibit a slight difference in catalytic oxidation of organic pollutants due to comprehensive influencing factors, including their valence band position, reactive oxygen species, and pore structure properties related to the adsorption–reaction–desorption process. But the catalytic reduction ability of CO2 is obviously different due to the large differences of interaction between the surface of crystal structures and CO2 molecules, which are critical to determine the catalytic performance and reaction pathways. The enhanced adsorption and activation of CO2 on the α-Ga2O3 surface could promote the reduction reaction efficiency. Moreover, the large energy barrier of CH2* formation on β-Ga2O3 makes the formation of methane (CH4) relatively difficult compared to that on α-Ga2O3. The yield rate of CH4 (1.8 μmol·g–1·h–1) on α-Ga2O3 is three times better than that on β-Ga2O3 (CH4: 0.6 μmol·g–1·h–1). The current findings can offer novel insights into the understanding of crystal-structure-dependent photocatalytic performances and the design of new catalysts applied in energy conversion and environmental purification by crystal structure-tuning.

show abstract

Photoelectrochemical investigation of the role of surface-modified Yb species in the photocatalytic conversion of CO2 by H2O over Ga2O3 photocatalysts

Cited by 9 publications

References 40 publications

Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

Inside‐and‐Out Semiconductor Engineering for CO₂ Photoreduction: From Recent Advances to New Trends

Crystal-Structure-Dependent Photocatalytic Redox Activity and Reaction Pathways over Ga₂O₃ Polymorphs

Contact Info

Product

Resources

About

Photoelectrochemical investigation of the role of surface-modified Yb species in the photocatalytic conversion of CO2 by H2O over Ga2O3 photocatalysts

Cited by 9 publications

References 40 publications

Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

Inside‐and‐Out Semiconductor Engineering for CO2 Photoreduction: From Recent Advances to New Trends

Crystal-Structure-Dependent Photocatalytic Redox Activity and Reaction Pathways over Ga2O3 Polymorphs

Contact Info

Product

Resources

About

Inside‐and‐Out Semiconductor Engineering for CO₂ Photoreduction: From Recent Advances to New Trends

Crystal-Structure-Dependent Photocatalytic Redox Activity and Reaction Pathways over Ga₂O₃ Polymorphs