Research progress on methane conversion coupling photocatalysis and thermocatalysis

Zhu, Zengzan; Guo, Wenyi; Zhang, Ying; Pan, Chengsi; Xu, Jing; Zhu, Yongfa; Lou, Yang

doi:10.1002/cey2.127

Cited by 79 publications

(62 citation statements)

References 241 publications

(279 reference statements)

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“…153 Photocatalysis offers an efficient approach to drive thermodynamically nonspontaneous reactions under mild conditions. 373,374 Several oxides, sulfides, and carbonaceous semiconductors such as KNbO 3 , Cu 2 O, Bi 2 WO 6 , CdS, BiVO 4 , g-C 3 N 4 , CeO 2, etc., either in pristine form or cocatalysts have been investigated for the photocatalytic methane oxidation in aerobic conditions; however, the quantum efficiency of mentioned systems remains too low. 373,375−380 Interestingly, zinc-based photocatalysts demonstrated a high affinity for CH 4 activation.…”

Section: Photoactive Sacs For Ch 4 Ormentioning

confidence: 99%

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Kumar

Al‐Attas

et al. 2022

ACS Nano

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Direct conversion of methane (CH 4 ) to C 1−2 liquid oxygenates is a captivating approach to lock carbons in transportable value-added chemicals, while reducing global warming. Existing approaches utilizing the transformation of CH 4 to liquid fuel via tandemized steam methane reforming and the Fischer−Tropsch synthesis are energy and capital intensive. Chemocatalytic partial oxidation of methane remains challenging due to the negligible electron affinity, poor C−H bond polarizability, and high activation energy barrier. Transition-metal and stoichiometric catalysts utilizing harsh oxidants and reaction conditions perform poorly with randomized product distribution. Paradoxically, the catalysts which are active enough to break C−H also promote overoxidation, resulting in CO 2 generation and reduced carbon balance. Developing catalysts which can break C−H bonds of methane to selectively make useful chemicals at mild conditions is vital to commercialization. Single atom catalysts (SACs) with specifically coordinated metal centers on active support have displayed intrigued reactivity and selectivity for methane oxidation. SACs can significantly reduce the activation energy due to induced electrostatic polarization of the C−H bond to facilitate the accelerated reaction rate at the low reaction temperature. The distinct metal−support interaction can stabilize the intermediate and prevent the overoxidation of the reaction products. The present review accounts for recent progress in the field of SACs for the selective oxidation of CH 4 to C 1−2 oxygenates. The chemical nature of catalytic sites, effects of metal−support interaction, and stabilization of intermediate species on catalysts to minimize overoxidation are thoroughly discussed with a forward-looking perspective to improve the catalytic performance.

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Section: Photoactive Sacs For Ch 4 Ormentioning

confidence: 99%

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Kumar

Al‐Attas

et al. 2022

ACS Nano

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“…Therefore, efficiently converting methane to value‐added chemicals is of great significance. [ 296 ]…”

Section: Selective Oxidation Over Sacsmentioning

confidence: 99%

“…Therefore, efficiently converting methane to value-added chemicals is of great significance. [296] The first C-H bond in the methane molecule has extremely high bond energy (439.3 kJ mol −1 ), [297,298] which makes its cleavage (homolysis or heterolysis) very difficult. Currently, the indirect methane converting pathways include steam reforming of methane (SRM) and dry reforming of methane (DRM), in which thermal energy provides a large amount of energy to split C-H bonds, resulting in high energy costs.…”

Section: Selective Oxidation Of Methane To C1 Oxygenatesmentioning

confidence: 99%

“…Currently, the indirect methane converting pathways include steam reforming of methane (SRM) and dry reforming of methane (DRM), in which thermal energy provides a large amount of energy to split C-H bonds, resulting in high energy costs. [296,[299][300][301][302][303] Meanwhile, the target product is prone to further over-oxidation to CO 2 , resulting in low selectivity. Converting methane by direct routes has been investigated from the aspects of enzyme catalysis, [304][305][306][307][308][309] homogeneous catalysis, [310][311][312] and heterogeneous catalysis.…”

Section: Selective Oxidation Of Methane To C1 Oxygenatesmentioning

confidence: 99%

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Homogeneity of Supported Single‐Atom Active Sites Boosting the Selective Catalytic Transformations

et al. 2022

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Selective conversion of specific functional groups to desired products is highly important but still challenging in industrial catalytic processes. The adsorption state of surface species is the key factor in modulating the conversion of functional groups, which is correspondingly determined by the uniformity of active sites. However, the non‐identical number of metal atoms, geometric shape, and morphology of conventional nanometer‐sized metal particles/clusters normally lead to the non‐uniform active sites with diverse geometric configurations and local coordination environments, which causes the distinct adsorption states of surface species. Hence, it is highly desired to modulate the homogeneity of the active sites so that the catalytic transformations can be better confined to the desired direction. In this review, the construction strategies and characterization techniques of the uniform active sites that are atomically dispersed on various supports are examined. In particular, their unique behavior in boosting the catalytic performance in various chemical transformations is discussed, including selective hydrogenation, selective oxidation, Suzuki coupling, and other catalytic reactions. In addition, the dynamic evolution of the active sites under reaction conditions and the industrial utilization of the single‐atom catalysts are highlighted. Finally, the current challenges and frontiers are identified, and the perspectives on this flourishing field is provided.

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“…Nevertheless, like other semiconductors, pristine MHPs also suffer from severe charge recombination, and meanwhile, their activity for photocatalytic CO 2 reduction is yet pretty low. Very recently, a few attempts have been successfully made to enhance the photocatalytic performance of MHPs, [19,20] such as building a Schottky barrier with metals, [21] creating type II or Z-scheme heterostructures with other semiconductors, [22][23][24][25] coupling with conductive reduced graphene oxide (r-GO), [26] and others. However, these hybrid MHPs were generally prepared by physically mixing or assembly method.…”

Section: Introductionmentioning

confidence: 99%

In‐Situ Generated CsPbBr₃ Nanocrystals on O‐Defective WO₃ for Photocatalytic CO₂ Reduction

et al. 2022

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Metal halide perovskite (MHP) nanocrystals (NCs) have shown promising application in photocatalytic CO2 reduction, but their activities are still largely restrained by severe charge recombination and narrow solar spectrum response. Assembly of heterojunctions can be beneficial to the charge separation in MHPs while the assembly process usually brings native interfacial defects, impeding efficient charge separation between two materials. Herein, an in‐situ generation strategy was developed to prepare CsPbBr3/WO3 heterojunction, using WO3 nanosheets (NSs) as growing substrate for the growth of CsPbBr3 NCs. The developed CsPbBr3/WO3 heterojunction exhibited a high‐quality interface, greatly facilitating charge transfer between two semiconductors. The hybrid photocatalyst displayed an excellent activity toward CO2 reduction, which was about 7‐fold higher than pristine CsPbBr3 NCs and 3.5‐fold higher than their assembled counterparts. The experimental results and theoretical simulations revealed that a Z‐scheme mechanism with a favorable internal electric field was responsible for the good performance of CsPbBr3/WO3 heterojunction. By using O‐defective WO3 NSs as a near‐infrared (NIR) light absorber, the CsPbBr3/WO3 heterojunction could harvest NIR light and showed an impressive activity toward CO2 reduction. This work demonstrates a new strategy to design MHP‐based heterojunctions by synergistically considering the interface quality, charge transfer mode, interfacial electric field, and light response range between two semiconductors.

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Research progress on methane conversion coupling photocatalysis and thermocatalysis

Cited by 79 publications

References 241 publications

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Homogeneity of Supported Single‐Atom Active Sites Boosting the Selective Catalytic Transformations

In‐Situ Generated CsPbBr₃ Nanocrystals on O‐Defective WO₃ for Photocatalytic CO₂ Reduction

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Research progress on methane conversion coupling photocatalysis and thermocatalysis

Cited by 79 publications

References 241 publications

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Homogeneity of Supported Single‐Atom Active Sites Boosting the Selective Catalytic Transformations

In‐Situ Generated CsPbBr3 Nanocrystals on O‐Defective WO3 for Photocatalytic CO2 Reduction

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In‐Situ Generated CsPbBr₃ Nanocrystals on O‐Defective WO₃ for Photocatalytic CO₂ Reduction