Sustainable production of hydrogen with high purity from methanol and water at low temperatures

Zhang, Sai; Liu, Yuxuan; Zhang, Mingkai; Ma, Yuanyuan; Hu, Jun; Qu, Yongquan

doi:10.1038/s41467-022-33186-z

Cited by 61 publications

(46 citation statements)

References 58 publications

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“…As a typical reducible oxide, CeO 2 as active catalyst or additive has been widely investigated for the catalytic reactions involving H 2 O. − As shown in Figure a, the H 2 O molecule is stably adsorbed on the ideal CeO 2 (110) surface, in which O and H atoms of H 2 O bond with Ce and O atoms of CeO 2 , respectively. With this adsorption configuration, the energy barrier of H 2 O dissociation on ideal CeO 2 (110) is 0.58 eV, which is significantly lower than the barrier of 1.12 eV on Pt(111) . Benefiting from the relatively large space between the Lewis acid and Lewis base, the adsorption of H 2 O molecules on the FLP sites induces a significantly closer distance between H 2 O molecules and the surface of CeO 2 (Figure b).…”

Section: Embedded Adsorption Configuration Of Small Molecules On Flp ...mentioning

confidence: 94%

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Zhang

Tian

et al. 2023

ACS Catal.

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Adsorption of molecules on active sites of heterogeneous catalysts significantly affects their catalytic performance, which provides a perspective to understand the catalytic process/mechanism at the atomic level and to establish structure–function relationships. This Perspective illustrates a strong correlation between the adsorption of reactants on CeO2-based catalysts and their improved catalytic activity and/or selectivity for various transformations. Regulating the oxygen defect of CeO2 provides an effective approach to construct two typical active sites of a frustrated Lewis pair (FLP) and dual-active site. Benefiting from the unique spatial and electronic structures, the FLP sites exhibit an “embedded” adsorption configuration of small molecules, promoting their effective activation and transformation. The dual-active sites constructed by metal clusters and oxygen vacancy of CeO2 could break the competitive adsorption of various molecules and thereafter enable highly active and selective hydrogenations. Finally, the possibilities and challenges in the adsorption behaviors of various molecules on CeO2-based catalysts are outlined. The tailorability of adsorption strength and selective configuration of molecules on active sites are anticipated to stimulate and guide the design of high-performing catalysts.

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Section: Embedded Adsorption Configuration Of Small Molecules On Flp ...mentioning

confidence: 94%

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Zhang

Tian

et al. 2023

ACS Catal.

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“…In addition, ab initio molecular dynamics (AIMD) simulations were performed to investigate the stability of the SA-FLP catalysts, which shows that SA-FLP-2 and SA-FLP-3 are relatively stable and can maintain FLP sites at high temperatures (Figure S2). Furthermore, several groups have recently synthesized Pt 1 @CeO 2 catalysts with different morphologies, 24,49 indicating that the synthesis of the SA-FLP dual-active site catalyst is possible in the experiments. Subsequently, the dissociative activation of methane was investigated on SA-FLP-2 and SA-FLP-3.…”

Section: Effect Of Oxygen Vacancy Concentration On Methane Activationmentioning

confidence: 99%

Design of SA-FLP Dual Active Sites for Nonoxidative Coupling of Methane

Ban

Kang

et al. 2023

ACS Catal.

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Direct conversion of methane to value-added chemical products under nonoxidative conditions is one of the most effective routes but still faces eminent challenges due to thermodynamic constraints and the lack of efficient catalysts. Herein, we propose to construct “Single-Atom”-“Frustrated Lewis Pair” (SA-FLP) dual-active-site catalysts for nonoxidative coupling of methane (NOCM). The single-atom site is created by doping a Pt atom at the Ce site of the CeO2 surface. The FLP site is fabricated by removing oxygen atom(s) adjacent to Pt atoms. Density functional theory (DFT) calculations reveal that SA-FLP dual active sites can simultaneously activate two methane molecules and notably enhance the coupling of hydrocarbon species to generate C2 products. The SA-FLP sites with two oxygen vacancies show the best performance for methane activation with a low energy barrier of 0.32 and 0.71 eV at SA and FLP sites, respectively. The coupling of two methyl groups to further generate ethane and ethylene only needs to surpass the highest barrier of 1.31 eV. Microkinetic analysis demonstrates that on the designed SA-FLP sites, CH4 consumption can reach a high turnover frequency (TOF) of 0.3014 s–1 under the conditions of 1200 K and a CH3 partial pressure of 8.0 × 10–3 bar, which is nearly two orders of magnitude higher than the experimentally reported value (3.8 ∼ 5.5 × 10–3 s–1) on traditional Pt/CeO2 catalysts. Importantly, the main product on the SA-FLP sites is shown to be the desired ethane with a TOF of 0.2535 s–1 under the conditions mentioned above. This study not only provides a strategy for designing efficient catalysts for NOCM but also offers insights into C–C coupling to generate oriented C2 products.

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“…Similarly, CeO 2 (110) presents the highest possibility for FLPs construction ( Huang, 2016 ; Zhang et al, 2017 ). Many studies have proposed that FLPs constructed on defective ceria possess high activities for many small-molecule activation (such as, H 2 , NO, CO 2 ) ( Mo et al, 2015 ; Stephan and Erker, 2015 ; Huang et al, 2018 ; Li J. et al, 2021 ; Li et al, 2022 ; Zhang et al, 2022 ; Zou et al, 2022 ). Qu’s group have explored the adsorption and activation of CO 2 on CeO 2 (110) surface by DFT calculations and found that CO 2 can be easily activated on defective CeO 2 and further activated on FLPs because of the more negatively charged oxygen of CO 2 , when compared to CO 2 on an ideal CeO 2 (110) surface ( Figure 6A ) ( Zhang et al, 2019 ).…”

Section: Electronic Properties Of Ceo 2 -Based Nan...mentioning

confidence: 99%

“…Furthermore, they synthesized a porous nanorods of CeO 2 ( PN -CeO 2 ) with a high surface Ce 3+ fraction and obtained an improved selectivity of 94% for cyclic carbonates. Subsequently, Zhang et al have designed a single-atom Pt anchored PN -CeO 2 catalyst (Pt 1 / PN -CeO 2 ) with dual-active sites of Pt single-atoms and FLPs on PN -CeO 2 to ensure the effective activation of both CH 3 OH and H 2 O for high efficient H 2 generation at low temperatures ( Figure 6E ) ( Zhang et al, 2022 ).…”

Section: Electronic Properties Of Ceo 2 -Based Nan...mentioning

confidence: 99%

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Recent advances and perspectives of CeO2-based catalysts: Electronic properties and applications for energy storage and conversion

Wang

Sun

et al. 2022

Front. Chem.

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Cerium dioxide (CeO2, ceria) has long been regarded as one of the key materials in modern catalysis, both as a support and as a catalyst itself. Apart from its well-established use (three-way catalysts and diesel engines), CeO2 has been widely used as a cocatalyst/catalyst in energy conversion and storage applications. The importance stems from the oxygen storage capacity of ceria, which allows it to release oxygen under reducing conditions and to store oxygen by filling oxygen vacancies under oxidizing conditions. However, the nature of the Ce active site remains not well understood because the degree of participation of f electrons in catalytic reactions is not clear in the case of the heavy dependence of catalysis theory on localized d orbitals at the Fermi energy EF. This review focuses on the catalytic applications in energy conversion and storage of CeO2-based nanostructures and discusses the mechanisms for several typical catalytic reactions from the perspectives of electronic properties of CeO2-based nanostructures. Defect engineering is also summarized to better understand the relationship between catalytic performance and electronic properties. Finally, the challenges and prospects of designing high efficiency CeO2-based catalysts in energy storage and conversion have been emphasized.

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Sustainable production of hydrogen with high purity from methanol and water at low temperatures

Cited by 61 publications

References 58 publications

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Design of SA-FLP Dual Active Sites for Nonoxidative Coupling of Methane

Recent advances and perspectives of CeO2-based catalysts: Electronic properties and applications for energy storage and conversion

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Sustainable production of hydrogen with high purity from methanol and water at low temperatures

Cited by 61 publications

References 58 publications

Adsorption of Molecules on Defective CeO2 for Advanced Catalysis

Adsorption of Molecules on Defective CeO2 for Advanced Catalysis

Design of SA-FLP Dual Active Sites for Nonoxidative Coupling of Methane

Recent advances and perspectives of CeO2-based catalysts: Electronic properties and applications for energy storage and conversion

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Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis