Crystal structure engineering of metal halide perovskites for photocatalytic organic synthesis

Wang, Chunhua; Ding, Yang; Liu, Biao; Weng, Bo; Hofkens, Johan; Roeffaers, Maarten

doi:10.1039/d3cc00468f

Cited by 18 publications

(6 citation statements)

References 30 publications

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“…According to the function E g = E VB – E CB , the VB potentials ( E VB ) of CdS and ZnIn 2 S 4 are calculated to be about 1.68 and 2.15 V (vs NHE), respectively. Obviously, both CdS and ZnIn 2 S 4 have capacities for reducing CO 2 into CO (−0.53 V) and oxidizing ArCH 2 OH into ArCHO (1.6 V) (Figure e) . In other words, this dual-function redox reaction system is feasible in thermodynamics.…”

Section: Resultsmentioning

confidence: 99%

“…Obviously, both CdS and ZnIn 2 S 4 have capacities for reducing CO 2 into CO (−0.53 V) 46 and oxidizing ArCH 2 OH into ArCHO (1.6 V) (Figure 6e). 47 In other words, this dualfunction redox reaction system is feasible in thermodynamics. On the other hand, the staggered energy level structure is formed between CdS and ZnIn 2 S 4 (Figure 6e).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Tailoring Charge Separation in ZnIn₂S₄@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO₂ Reduction under Visible Light

Wang,

Pu,

et al. 2024

Inorg. Chem.

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Artificial photosynthesis provides a sustainable strategy for producing usable fuels and fine chemicals and attracts broad research interest. However, conventional approaches suffer from low reactivity or low selectivity. Herein, we demonstrate that photocatalytic reduction of CO 2 coupled with selective oxidation of aromatic alcohol into corresponding syngas and aromatic aldehydes can be processed efficiently and fantastically over the designed S-scheme ZnIn 2 S 4 @CdS core−shell hollow nanocage under visible light. In the ZnIn 2 S 4 @CdS heterostructure, the photoexcited electrons and holes with weak redox capacities are eliminated, while the photoexcited electrons and holes with powder redox capacities are separated spatially and preserved on the desired active sites. Therefore, even if there are no cocatalysts and no vacancies, ZnIn 2 S 4 @CdS exhibits high reactivity. For instance, the CO production of ZnIn 2 S 4 @CdS is about 3.2 and 3.4 times higher than that of pure CdS and ZnIn 2 S 4 , respectively. More importantly, ZnIn 2 S 4 @CdS exhibits general applicability and high photocatalytic stability. Trapping agent experiments, 13 CO 2 isotopic tracing, in situ characterizations, and theoretical calculations reveal the photocatalytic mechanism. This study provides a new strategy to design efficient and selective photocatalysts for dual-function redox reactions by tailoring the active sites and regulating vector separation of photoexcited charge carriers.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Tailoring Charge Separation in ZnIn₂S₄@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO₂ Reduction under Visible Light

Wang,

Pu,

et al. 2024

Inorg. Chem.

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“…In Figure 6c, the slopes of the Mott-Schottky curves for the CAU-17 and MIL-100(Fe) samples are positive, indicating that they are n-type semiconductors. Based on the Mott-Schottky plot, the flat-band (E fb ) potentials of CAU-17 and MIL-100(Fe) were calculated to be −0.2 and −0.38 eV versus SCE, which can be converted to −0.34 and −0.52 eV versus NHE [37]. Combining these values with the E g evaluated by the Tauc plots, the valence band potentials (E VB ) of CAU-17 and MIL-100(Fe) were estimated to be +3.55 and +1.85 eV vs. NHE by using Equation ( 2).…”

Section: Degradation Performancementioning

confidence: 99%

Rational Design of Z-Scheme Heterostructures Composed of Bi/Fe-Based MOFs for the Efficient Photocatalytic Degradation of Organic Pollutants

Xu,

Zhu,

Zhou

et al. 2024

Catalysts

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Metal–organic frameworks (MOFs) have recently gained attention as a highly promising category of photocatalytic materials, showing great potential in the degradation of organic dyes such as Rhodamine B (RhB). Nonetheless, the mono-metal MOF materials in this application are often constrained by their limited light absorption capabilities and their propensity for recombination with carriers. The combination of different metal-based MOFs to form heterogeneous reactors could present a promising approach for the removal of dyes from water. In this work, a new CAU-17/MIL-100(Fe) Z-scheme heterojunction photocatalyst composed of two MOFs with the same ligands is reported to realize the efficient degradation of dyes in water. The combination of the two MOFs results in a significant enhancement of the surface open sites, optical responsivity range, and charge-separating efficiency through synergistic effects. In addition, the capture experiments conducted on the photocatalytic process have verified that ∙O2− and h+ are the primary active species. Consequently, CAU-17/MIL-100(Fe) exhibited excellent photocatalytic activity and stability. The degradation rate of the optimal CAU-17/MIL-100(Fe) photocatalyst was 34.55 times that of CAU-17 and 3.60 times that of MIL-100(Fe). Our work provides a new strategy for exploring the visible-light degradation of RhB in bimetallic MOF composites.

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“…13.2. Cs 3 Bi 2 Br 9 /Pd Heterostructures Roeffaers and co-workers reported the development of Schottky junction-type heterostructures involving lead-free Cs 3 Bi 2 Br 9 and Pd for benzyl alcohol oxidation and H 2 generation [135,136]. They achieved this by using crystalline Cs 3 Bi 2 Br 9 as the core material, complemented by amorphous Pd nanocubes forming the outer shell.…”

Section: Lead-free Cs3bi2br9 Perovskitesmentioning

confidence: 99%

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations

Jagadeeswararao,

Galian,

Pérez-Prieto

2023

Nanomaterials

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Heterogeneous photocatalysts incorporating metal halide perovskites (MHPs) have garnered significant attention due to their remarkable attributes: strong visible-light absorption, tuneable band energy levels, rapid charge transfer, and defect tolerance. Additionally, the promising optical and electronic properties of MHP nanocrystals can be harnessed for photocatalytic applications through controlled crystal structure engineering, involving composition tuning via metal ion and halide ion variations, dimensional tuning, and surface chemistry modifications. Combination of perovskites with other materials can improve the photoinduced charge separation and charge transfer, building heterostructures with different band alignments, such as type-II, Z-scheme, and Schottky heterojunctions, which can fine-tune redox potentials of the perovskite for photocatalytic organic reactions. This review delves into the activation of organic molecules through charge and energy transfer mechanisms. The review further investigates the impact of crystal engineering on photocatalytic activity, spanning a diverse array of organic transformations, such as C–X bond formation (X = C, N, and O), [2 + 2] and [4 + 2] cycloadditions, substrate isomerization, and asymmetric catalysis. This study provides insights to propel the advancement of metal halide perovskite-based photocatalysts, thereby fostering innovation in organic chemical transformations.

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Crystal structure engineering of metal halide perovskites for photocatalytic organic synthesis

Abstract: Engineering crystal structure of Cs3BiBr6 and Cs3Bi2Br9 is theoretically and experimentally demonstrated to modulate their photocatalytic performance. This work offers insights into the structure-photoactivity relationships of metal halide perovskites (MHPs)...

Cited by 18 publications

References 30 publications

Tailoring Charge Separation in ZnIn₂S₄@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO₂ Reduction under Visible Light

Tailoring Charge Separation in ZnIn₂S₄@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO₂ Reduction under Visible Light

Rational Design of Z-Scheme Heterostructures Composed of Bi/Fe-Based MOFs for the Efficient Photocatalytic Degradation of Organic Pollutants

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations

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Crystal structure engineering of metal halide perovskites for photocatalytic organic synthesis

Abstract: Engineering crystal structure of Cs3BiBr6 and Cs3Bi2Br9 is theoretically and experimentally demonstrated to modulate their photocatalytic performance. This work offers insights into the structure-photoactivity relationships of metal halide perovskites (MHPs)...

Cited by 18 publications

References 30 publications

Tailoring Charge Separation in ZnIn2S4@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO2 Reduction under Visible Light

Tailoring Charge Separation in ZnIn2S4@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO2 Reduction under Visible Light

Rational Design of Z-Scheme Heterostructures Composed of Bi/Fe-Based MOFs for the Efficient Photocatalytic Degradation of Organic Pollutants

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations

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Tailoring Charge Separation in ZnIn₂S₄@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO₂ Reduction under Visible Light

Tailoring Charge Separation in ZnIn₂S₄@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO₂ Reduction under Visible Light