Cooperative selective benzyl alcohol oxidation and hydrogen production over Pd6(SC12H25)12cluster-coupled CdS nanorods: the key role of water in photocatalytic benzyl alcohol splitting

Luo, Dian; Luo, Yao; Lu, Xiangyu; Shi, Manman; Wei, Jieding; Lu, Zhou; Huang, Yucheng; Ni, Yonghong

doi:10.1039/d2ta04073e

Cited by 16 publications

(8 citation statements)

References 48 publications

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“…Subsequently, the cleavage of O‐H bonds occurs with the reaction of *C 6 H 5 CH 2 OH → *C 6 H 5 CH 2 O − (*BA1) + H + proceeds, which exhibits the highest free energy barrier, and is thus considered as the rate‐determining step (RDS) of the reaction. [ 29 ] Finally, with the breakage of C α ‐H bonds, another H + is further lost, forming C 6 H 5 CHO. For the above process, the free energy barrier of RDS for BiOCl MSCN is apparently lower than BiOCl NS‐1 (2.52 eV), only 2.13 eV, revealing the presence of oxygen vacancies is more thermodynamically favorable for BA oxidation.…”

Section: Resultsmentioning

confidence: 99%

Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

Mao

Liu

et al. 2023

Advanced Materials

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The photoresponse and photocatalytic efficiency of bismuth oxychloride (BiOCl) are greatly limited by rapid recombination of photogenerated carriers. The construction of porous single‐crystal BiOCl photocatalyst can effectively alleviate this issue and provide accessible active sites. Herein, a facile chelated ion‐exchange strategy is developed to synthesize BiOCl mesoporous single‐crystalline nanosheets (BiOCl MSCN) using acetic acid and ammonia solution respectively as chelating agent and ionization promoter. The strong chelation between acetate ions and Bi3+ ions introduces acetate ions into the precipitated product to exchange with Cl‐ ions, resulting in large lattice mismatch, strain release, and formation of void‐like mesopores. The prepared BiOCl MSCN photocatalyst exhibits excellent catalytic performance with 99% conversion and 98% selectivity for oxidation of benzyl alcohol to benzaldehyde and superior general adaptability for various aromatic alcohols. The theoretical calculations and characterizations confirm that the superior performance is mainly attributed to the abundant oxygen vacancies, plenty of accessible adsorption/active sites and fast charge transport path without grain boundaries.

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Section: Resultsmentioning

confidence: 99%

Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

Mao

Liu

et al. 2023

Advanced Materials

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“…Femtosecond Time-Resolved Transient Absorption Spectroscopy: The femtosecond pump-probe transient absorption (TA) spectrometer based on a 1 KHz Ti: sapphire laser amplification system (Spitfire Ace, Spectra Physics) was described elsewhere. [23,24] Briefly, a portion of the output beam with a center wavelength of 800 nm and a pulse width of 80 fs from the amplifier was guided into an optical parametric amplification system (TOPAS Prime, Light Conversion) to produce the femtosecond pump beam with tunable wavelength, while another part of the laser beam was focused into a CaF 2 crystal to generate the white light continuum (350-700 nm) to serve as the probe beam. The pump (360 nm, 200 nJ per pulse) and probe beams overlapped in a 2 mm fused silica cuvette where the samples were dispersed in water at a concentration of 0.5 mg mL −1 .…”

Section: Methodsmentioning

confidence: 99%

π‐Conjugated In‐Plane Heterostructure Enables Long‐Lived Shallow Trapping in Graphitic Carbon Nitride for Increased Photocatalytic Hydrogen Generation

Zhang

Ren

et al. 2023

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the development of semiconductor-based photocatalysts that can efficiently split water for durable photocatalytic H 2 production is at the forefront. To date, among numerous photocatalysts that have been demonstrated for H 2 production under exposure to UV and visible light, [4][5][6]56] conjugated graphitic carbon nitride has stood out as one of the most investigated photocatalysts in the past decade owing to the advantages of its suitable energy position for water splitting, visible light harvesting, easy functionalization, and facile preparation from low-cost precursors. [7,55] Nevertheless, pristine g-CN suffers from an exceptionally high charge carrier recombination rate primarily due to the relatively short-lived excited states, such as nascent excitons and shallow trapping states, [8] which results in a low photocatalytic performance. Kinetics studies by ultrafast time-resolved spectroscopy reveal three allowable trapping processes for photoinduced charge carriers in g-CN, including short-lived excitons, shallow trapping states, and deep trapping states. [9,10] Among them, the short-lived excitons and the charges in the shallow trap states play a crucial role in photoactivity enhancement. Hence, increasing the decay lifetime of the excitons and shallow trapping in g-CN are expected to enhance the photocatalytic performance yet less investigated.To date, many strategies have been applied to modulate the photoinduced charge-carrier trapping process in g-CN viaThe relatively short-lived excited states, such as the nascent electron-hole pairs (excitons) and the shallow trapping states, in semiconductor-based photocatalysts produce an exceptionally high charge carrier recombination rate, dominating a low solar-to-fuel performance. Here, a π-conjugated in-plane heterostructure between graphitic carbon nitride (g-CN) and carbon rings (C rings ) (labeling g-CN/C rings ) is effectively synthesized from the thermolysis of melamine-citric acid aggregates via a microwave-assisted heating process. The g-CN/C rings in-plane heterostructure shows remarkably suppressed excited-state decay and increased charge carrier population in photocatalysis. Kinetics analysis from the femtosecond time-resolved transient absorption spectroscopy illustrates that the g-CN/C rings π-conjugated heterostructure produces slower exciton annihilation (τ 1 = 7.9 ps) and longer shallow electron trapping (τ 2 = 407.1 ps) than pristine g-CN (τ 1 = 3.6 ps, τ 2 = 264.1 ps) owing to C rings incorporation, both of which enable more photoinduced electrons to participate in the photocatalytic reactions, thereby realizing photoactivity enhancement. As a result, the photocatalytic activity exhibits an eightfold enhancement in visible-light-driven H 2 generation. This work provides a viable route of constructing π-conjugated in-plane heterostructures to suppress the excited-state decay and improve the photocatalytic performance.

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“…The deposition of secondary components such as cocatalysts and heterojunction formation allow the photoreforming selectivity to be tuned to favor the generation of aldehydes or C–C coupling products. Numerous types of photocatalysis have been developed for the highly selective formation of aldehydes, with recent high-efficiency photocatalysts achieving selectivity of ≥90%. − The hydrogen generated when photocatalysts are used for benzyl alcohol conversion is also favorable; for example, Hao et al developed nickel-sulfide-decorated zinc sulfide nanorods for the photocatalytic transformation of benzyl alcohol to benzaldehyde coupled with H 2 evolution …”

Section: Introductionmentioning

confidence: 99%

“…Numerous studies have confirmed that the oxidative ability of the catalyst is primarily enhanced via the use of cocatalyst systems, which improve transformation efficiency and selectivity. − …”

Section: Introductionmentioning

confidence: 99%

Tunable Selectivity of Photocatalytic Benzyl Alcohol Transformation over Ag-Ion-Exchanged CdS Nanowires

Kang

Lee

et al. 2023

ACS Sustainable Chem. Eng.

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Existing methods for the photocatalytic transformation of aromatic alcohols to value-added products via C−C cross-coupling are inefficient and insufficiently selective. Herein, a series of cadmium sulfide nanowires (CdS NWs) loaded with Ag 2 S (denoted as Ag 2 S@CdS NWs) are constructed via a simple Ag + exchange protocol for the photocatalytic transformation of benzyl alcohol. We successfully demonstrated that the selectivity toward specific products in the photocatalytic transformation of benzyl alcohol over Ag +exchanged CdS NWs is controlled by varying the amount of exchanged Ag + ions. Notably, the product of the photocatalytic reaction was dependent on the amount of Ag + ions exchanged: with a Ag + exchange of <5 mol %, the C−C coupling product was obtained with >90% selectivity and >95% transformation yield owing to photoinduced electron transfer from the conduction band of CdS to Ag 2 S. Conversely, with a Ag + exchange of >7 mol %, a cocatalyst in which Ag 2 S and Ag are mixed was produced, and benzaldehyde was obtained with >90% selectivity and >90% transformation yield because of photoinduced hole transfer from the valence band of CdS to Ag 2 S/Ag. This study proves that Ag 2 S@CdS NWs can be used as a basis for the development of heterojunction photocatalysts for the conversion of aromatic alcohols into value-added products via C− C cross-coupling reactions or photooxidation toward aromatic aldehyde.

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Cooperative selective benzyl alcohol oxidation and hydrogen production over Pd₆(SC₁₂H₂₅)₁₂cluster-coupled CdS nanorods: the key role of water in photocatalytic benzyl alcohol splitting

Abstract: Photocatalytic splitting of alcohols into hydrogen and corresponding carbonyl compounds has potential applications in the production of clean H2 fuel and high-value chemicals using solar light as the sole energy...

Cited by 16 publications

References 48 publications

Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

π‐Conjugated In‐Plane Heterostructure Enables Long‐Lived Shallow Trapping in Graphitic Carbon Nitride for Increased Photocatalytic Hydrogen Generation

Tunable Selectivity of Photocatalytic Benzyl Alcohol Transformation over Ag-Ion-Exchanged CdS Nanowires

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