Design of frustrated Lewis pair in defective TiO2 for photocatalytic non-oxidative methane coupling

Ma, Jiayu; Zhang, Qingqing; Chen, Ziyu; Kang, Kai; Pan, Lihan; Wu, Shiqun; Chen, Chen; Wu, Zhiqin; Zhang, Jinlong; Wang, Lingzhi

doi:10.1016/j.checat.2022.05.016

Cited by 17 publications

(18 citation statements)

References 64 publications

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“…It has theoretically proven that FLP can help activate the C-H bond of methane but the efficient practical catalyst has been rarely reported 35 , 36 . We have recently tried to utilize coupled LA and LB on metal-doped reduced TiO 2 for promoting the photocatalytic NOCM, which however fails to break the records achieved by noble metal-containing systems 37 . The inconsistency between the theoretic calculation and practical activity should be attributed to the failure to construct abundant and easily accessible FLP sites during the catalyst preparation.…”

Section: Introductionmentioning

confidence: 99%

High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

Chen

Feng

et al. 2023

Nat Commun

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Photocatalytic methane conversion requires a strong polarization environment composed of abundant activation sites with the robust stretching ability for C-H scissoring. High-density frustrated Lewis pairs consisting of low-valence Lewis acid Nb and Lewis base Nb-OH are fabricated on lamellar Nb2O5 through a thermal-reduction promoted phase-transition process. Benefitting from the planar atomic arrangement of lamellar Nb2O5, the frustrated Lewis pairs sites are highly exposed and accessible to reactants, which results in a superior methane conversion rate of 1456 μmol g−1 h−1 for photocatalytic non-oxidative methane coupling without the assistance of noble metals. The time-dependent DFT calculation demonstrates the photo-induced electron transfer from LA to LB sites enhances their intensities in a concerted way, promoting the C-H cleavage through the coupling of LA and LB. This work provides in-depth insight into designing and constructing a polarization micro-environment for photocatalytic C-H activation of methane without the assistance of noble metals.

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Section: Introductionmentioning

confidence: 99%

High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

Chen

Feng

et al. 2023

Nat Commun

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“…Due to the strong sp 3 CÀ H bonds of CH 4 , methane activation under mild conditions is extremely challenging. Some research groups [56][57][58][59][60] have made efforts to investigate the reaction mechanisms of the activation of methane by FLP. However, in comparison with other small molecules, the reported examples of methane activation by FLP are particularly rare.…”

Section: Other Small Molecules Activationmentioning

confidence: 99%

Screening Carbon‐Boron Frustrated Lewis Pairs for Small‐Molecule Activation including N₂, O₂, CO, CO₂, CS₂, H₂O and CH₄: A Computational Study

Zeng

Qiu

Zhu

2023

Chemistry An Asian Journal

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Dinitrogen (N 2 ) activation is particularly challenging under ambient conditions because of its large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap (10.8 eV) and high bond dissociation energy (945 kJ mol À 1 ) of the N�N triple bond, attracting considerable attention from both experimental and theoretical chemists. However, most effort has focused on metallic systems. In contrast, nitrogen activation by frustrated Lewis pairs (FLPs) has been initiated recently via theoretical calculations. Here we perform density functional theory (DFT) calculations to screen a series of experimentally viable FLPs for small-molecule activation including N 2 , O 2 , CO, CO 2 , CS 2 , H 2 O and CH 4 . In addition, aromaticity is found to play an important role in most of these small-molecule activation. The particularly thermodynamic stabilities of the activation products and low reaction barriers could be a step forward for the development of FLP towards small-molecule activation including N 2 , inviting experimental chemists' verification.

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“…Metal oxides such as the FLP of γ-Al 2 O 3 (110) and CeO 2 (110) have a remarkable ability to activate the methane C-H bond [ 9 , 10 ], and nonoxidative C-C coupling can be performed on the surface of CeO 2 . Recently, researchers have extended the concept of FLP to multistage porous Ti-based and zeolite molecular sieve catalytic systems [ 11 , 12 ] and made important progress in the research of photocatalytic nonoxidative coupling of methane and dehydrogenation of hydrocarbons above C 3 . To date, the reference research methods and concepts are very limited.…”

Section: Introductionmentioning

confidence: 99%

Nonoxidative Coupling of Methane to Produce C2 Hydrocarbons on FLPs of an Albite Surface

et al. 2023

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The characteristics of active sites on the surface of albite were theoretically analyzed by density functional theory, and the activation of the C-H bond of methane using an albite catalyst and the reaction mechanism of preparing C2 hydrocarbons by nonoxidative coupling were studied. There are two frustrated Lewis pairs (FLPs) on the (001) and (010) surfaces of albite; they can dissociate H2 under mild conditions and show high activity for the activation of methane C-H bonds. CH4 molecules can undergo direct dissociative adsorption on the (010) surface, whereas a 50.07 kJ/mol activation barrier is needed on the (001) surface. The prepared albite catalyst has a double combination function of the (001) and (010) surfaces; these surfaces produce a spillover phenomenon in the process of CH4 activation reactions, where CH3 overflows from the (001) surface with CH3 adsorbed on the (010) surface to achieve nonoxidative high efficiently C-C coupling with an activation energy of 18.51 kJ/mol. At the same time, this spillover phenomenon inhibits deep dehydrogenation, which is conducive to the selectivity of the C2 hydrocarbons. The experimental results confirm that the selectivity of the C2 hydrocarbons is maintained above 99% in the temperature range of 873 K to 1173 K.

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Design of frustrated Lewis pair in defective TiO2 for photocatalytic non-oxidative methane coupling

Cited by 17 publications

References 64 publications

High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

Screening Carbon‐Boron Frustrated Lewis Pairs for Small‐Molecule Activation including N₂, O₂, CO, CO₂, CS₂, H₂O and CH₄: A Computational Study

Nonoxidative Coupling of Methane to Produce C2 Hydrocarbons on FLPs of an Albite Surface

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Design of frustrated Lewis pair in defective TiO2 for photocatalytic non-oxidative methane coupling

Cited by 17 publications

References 64 publications

High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

Screening Carbon‐Boron Frustrated Lewis Pairs for Small‐Molecule Activation including N2, O2, CO, CO2, CS2, H2O and CH4: A Computational Study

Nonoxidative Coupling of Methane to Produce C2 Hydrocarbons on FLPs of an Albite Surface

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Screening Carbon‐Boron Frustrated Lewis Pairs for Small‐Molecule Activation including N₂, O₂, CO, CO₂, CS₂, H₂O and CH₄: A Computational Study