Engineering ZnSn(OH)6 with ternary active sites-directed hydroxyl vacancies for robust deep C6H6 photo-oxidation: Experiment and DFT calculations

Li, Yuhan; Chen, Bangfu; Ouyang, Ping; Duan, Youyu; Ong, Wee‐Jun; Dong, Fan

doi:10.1016/j.cej.2022.138695

Cited by 10 publications

(3 citation statements)

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“…The values enable them to effectively react with adsorbed O 2 and H 2 O molecules, as well as −OH in the lattice of ZHS-M to generate • O 2 – (Figure ) and • OH E φ (O 2 /·O 2 – ) = −0.33 V, E φ (−OH/·OH) = 1.23 V, E φ (OH – /·OH) = 2.29 V, E φ ( • OH/OH – ) = 1.99 V, vs NHE, respectively (Figure S17a). Concurrently, • OH can undergo dimerization to form H 2 O 2 (Figure S17b), which can, in turn, be oxidized by a h + to produce • O 2 – …”

Section: Resultsmentioning

confidence: 99%

“…The values enable them to effectively react with adsorbed O 2 and H 2 O molecules, as well as −OH in the lattice of ZHS-M to generate • O 2 − (Figure 2) and S17a). 28 Concurrently, • OH can undergo dimerization to form H 2 O 2 (Figure S17b), which can, in turn, be oxidized by a h + to produce • O 2 − . 29 In general, (i) O 2 represents the principal active species for effecting the successful deep mineralization of C 7 H 8 and C 3 H 6 O in the process of photocatalytic oxidation and (ii) the outstanding fundamental properties of ZHS-M ensures its potential application in the photocatalytic oxidation of gaseous pollutants, such as C 7 H 8 and C 3 H 6 O in the atmosphere.…”

Section: Identification Of Crucialmentioning

confidence: 99%

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Synergistic Activation of Small Molecules and Free Radicals for the Deep Mineralization of Mixed VOCs

Chen,

Duan,

Chen

et al. 2024

ACS Catal.

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Deep mineralization of C 7 H 8 is often impeded by an ambiguous understanding of the key contributors to active species and the mechanism of benzene ring activation. Herein, the implementation of ZnSn(OH) 6 as a photocatalyst for the degradation of a mixture of C 7 H 8 and C 3 H 6 O aims to investigate the synergistic activation effects between small molecules and reactive free radicals. Upon irradiation, the catalyst exhibits a remarkable average decomposition efficiency of 98.42% toward the mixture (C 7 H 8 :C 3 H 6 O = 50:20 ppm), with a 97.8% degradation rate for C 7 H 8 and a 100% degradation rate for C 3 H 6 O. The molecular O 2 is the main active species for the photocatalytic oxidation of C 7 H 8 and C 3 H 6 O. Especially, activated C 7 H 8 and C 3 H 6 O undergo direct dehydrogenative cross-coupling in a radical state to produce the key intermediate C 10 H 12 O. Compared with the primary intermediate benzyl alcohol (ΔG = +1.52 eV), C 10 H 12 O (ΔG = −0.47 eV) displays a lower ring-opening energy barrier under • O 2− attack, thereby facilitating the selectivity of the photocatalytic oxidation ring-opening reaction of C 7 H 8 and the photodegradation of the mixture. The present research delves into the collaborative interplay between small molecules and reactive free radicals during the mineralization process of C 7 H 8 , thereby shedding light on innovative strategies for the efficient treatment of mixed polluted gases under real-world conditions.

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Section: Resultsmentioning

confidence: 99%

Section: Identification Of Crucialmentioning

confidence: 99%

Synergistic Activation of Small Molecules and Free Radicals for the Deep Mineralization of Mixed VOCs

Chen,

Duan,

Chen

et al. 2024

ACS Catal.

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“…Therefore, the potential application of multi-oxides in photocatalysis has received extensive attention. Zinc hydroxy stannate (ZnSn(OH) 6 ), as a precursor of the traditional piezoelectric material ZnSnO 3 , also possesses piezoelectricity and has been widely used in flame retardancy and gas detection due to its intrinsic characteristics such as high and stable activity and excellent gas sensitivity. , Notably, ZSH possesses abundant hydroxyl groups, which are theoretically capable of accepting photogenerated holes to yield a great deal of active hydroxyl radicals, and thus has a great potential for application in photocatalytic degradation of organics, H 2 production, and CO 2 reduction . Unfortunately, the wide bandgap energy of ZSH makes it only use part of ultraviolet light, which only accounts for 4% of sunlight. , …”

Section: Introductionmentioning

confidence: 99%

Piezoelectric Polarization and Sulfur Vacancy Enhanced Photocatalytic Hydrogen Evolution Performance of Bi₂S₃/ZnSn(OH)₆ Piezo-photocatalyst

Li,

Zhu,

Huang

et al. 2024

Inorg. Chem.

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The combination of piezoelectric catalysis and photocatalysis could effectively enhance the carrier separation efficiency and further improve the hydrogen production activity. However, piezoelectric polarization always suffers from a low polarization strength, which severely restricts its actual applications. In this study, we successfully synthesized a novel sulfur vacancy-rich Bi 2 S 3 /ZnSn (OH) 6 (BS-12/ZSH) piezo-photocatalyst for hydrogen evolution through water splitting. Notably, the piezo-photocatalytic hydrogen generation rate of the 8% BS-12/ ZSH catalyst (336.21 μmol/g/h) was superior to that of pristine ZSH (29.71 μmol/g/h) and BS-12 (21.66 μmol/g/h). In addition, the hydrogen generation for 8% BS-12/ZSH (336.21 μmol/g/h) under ultrasonic coupling illumination was significantly higher than that under single illumination (52.09 μmol/g/h) and ultrasound (121.90 μmol/g/h), owing to the cooperative interaction of the sulfur vacancy and piezoelectric field. Various characterization analyses confirmed that (1) the introduction of sulfur vacancies in BS-12 provided more active sites, (2) BS-12 with sulfur vacancies acted as a co-catalyst to accelerate the hydrogen production rate, and (3) the piezoelectric field eliminated the electrostatic shielding and offered an additional driving force, which effectively promoted the separation of electron−hole pairs. This research clearly reveals the synergistic effect between piezocatalysis and photocatalysis as well as offers a promising sight for the rational design of high-efficiency piezo-photocatalysts.

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Water‐Resistance‐Based S‐Scheme Heterojunction for Deep Mineralization of Toluene

Li,

Chen,

Liu

et al. 2024

Angewandte Chemie

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Deep mineralization of low concentration toluene (C7H8) is one of the most significant but challenging reactions in photocatalysis. It is generally assumed that hydroxyl radicals (·OH) as the main reactive species contribute to the enhanced photoactivity, however, it remains ambiguous at this stage. Herein, a S‐scheme ZnSn(OH)6‐based heterojunction with AlOOH as water resistant surface layer is in situ designed for tuning the free radical species and achieving deep mineralization of C7H8. By employing a combination of in situ DRIFTS and materials characterization techniques, we discover that the dominant intermediates such as benzaldehyde and benzoic acid instead of toxic phenols are formed under the action of holes (h+) and superoxide radicals (·O2‐). These dominant intermediates turn out to greatly decrease the ring‐opening reaction barrier. This study offers new possibilities for rationally tailoring the active species and thus directionally producing dominant intermediates via designing water resistant surface layer.

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Engineering ZnSn(OH)6 with ternary active sites-directed hydroxyl vacancies for robust deep C6H6 photo-oxidation: Experiment and DFT calculations

Cited by 10 publications

References 62 publications

Synergistic Activation of Small Molecules and Free Radicals for the Deep Mineralization of Mixed VOCs

Synergistic Activation of Small Molecules and Free Radicals for the Deep Mineralization of Mixed VOCs

Piezoelectric Polarization and Sulfur Vacancy Enhanced Photocatalytic Hydrogen Evolution Performance of Bi₂S₃/ZnSn(OH)₆ Piezo-photocatalyst

Water‐Resistance‐Based S‐Scheme Heterojunction for Deep Mineralization of Toluene

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Engineering ZnSn(OH)6 with ternary active sites-directed hydroxyl vacancies for robust deep C6H6 photo-oxidation: Experiment and DFT calculations

Cited by 10 publications

References 62 publications

Synergistic Activation of Small Molecules and Free Radicals for the Deep Mineralization of Mixed VOCs

Synergistic Activation of Small Molecules and Free Radicals for the Deep Mineralization of Mixed VOCs

Piezoelectric Polarization and Sulfur Vacancy Enhanced Photocatalytic Hydrogen Evolution Performance of Bi2S3/ZnSn(OH)6 Piezo-photocatalyst

Water‐Resistance‐Based S‐Scheme Heterojunction for Deep Mineralization of Toluene

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Piezoelectric Polarization and Sulfur Vacancy Enhanced Photocatalytic Hydrogen Evolution Performance of Bi₂S₃/ZnSn(OH)₆ Piezo-photocatalyst