Achieving efficient and robust catalytic reforming on dual-sites of Cu species

Ma, Kui; Tian, Ye; Zhao, Zhi‐Jian; Cheng, Qingpeng; Ding, Tao; Zhang, Jing; Zheng, Lirong; Jiang, Zheng; Abe, Takayuki; Tsubaki, Noritatsu; Gong, Jinlong; Li, Xingang

doi:10.1039/c9sc00015a

Cited by 76 publications

(31 citation statements)

References 44 publications

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“…show a slightly stronger white line relative to the Cu foil, indicating a predominant metallic Cu with a bit of Cu oxidation state. 24,25 The photon energy of adsorption edge is obviously lower than that of the Cu2O reference for the three samples (Fig. 3A, inset).…”

Section: Identification Of Cu δ+ -Ov−ti 3+ Interface Structurementioning

confidence: 88%

Identification of intrinsic active sites in ternary CuZnTi catalysts toward low-temperature water gas shift reaction

Zhang¹,

Yin²,

Xu³

et al. 2021

Preprint

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In the heterogeneous field, modulation over strong metal-support interactions (SMSI) plays a crucial role in boosting catalytic performance toward interface-sensitive reactions (e.g., water gas shift reaction, WGSR). Herein, a CuZnTi ternary catalyst was prepared via in situ structural topological transformation from CuZnTi-layered double hydroxides precursor (CuZnTi-LDHs). The resulting catalyst Cu/ZnTi-MMO(H350) exhibits an extraordinarily high catalytic activity toward low temperature-WGSR with a reaction rate of 19.7 μmolCO gcat-1 s-1 at 250 °C, among the highest level in Cu-based catalysts. Advanced electron microscope and in situ spectroscopy characterizations verify that Cu nanoparticles (particle size: 7~10 nm) are modified by ZnTi-mixed metal oxides with abundant Cuδ+−Ov−Ti3+ (0<δ<1) interfacial sites. Incorporation of Ti element facilitates the reduction of ZnO to stabilize Cuδ+ species at the interface, which enhances the chemisorption of CO molecule. Simultaneously, neighboring Ov−Ti3+ species significantly promotes the dissociation of H2O molecule. The structure-activity correlation studies based on quasi-in situ XPS, in situ DRIFTS, in situ and operando EXAFS reveal that the interfacial sites (Cuδ+−Ov−Ti3+) serve as the intrinsic active sites of WGS reaction. A combination of in situ characterization techniques and DFT calculations further substantiate that associative mechanism is the predominant reactive path below 200 °C whilst redox mechanism is overwhelming above 250 °C in the presence of Cu/ZnTi-MMO catalyst. This work demonstrates a facile modulation on metal-support interfacial structure via LDHs approach, which paves a way for rational design and preparation of heterogeneous catalysts.

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Section: Identification Of Cu δ+ -Ov−ti 3+ Interface Structurementioning

confidence: 88%

Identification of intrinsic active sites in ternary CuZnTi catalysts toward low-temperature water gas shift reaction

Zhang¹,

Yin²,

Xu³

et al. 2021

Preprint

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“…The mesopore encapsulation could hinder the migration of the large metal nanoparticles, but Ostwald ripening still works for the metal sintering. In order to further enhance the stability, Li and co‐workers synthesized metallic Cu nanoparticles surrounded by Cu 2 O species within the mesoporous silica ( Figure a–c). The Cu 2 O interacting with silica efficiently hindered the pathway for the diffusion of Cu species in Ostwald ripening, thus to give ideal sinter‐resistant catalysts in the hydrogen production from dimethyl ether reforming.…”

Section: Encapsulation Within Mesoporous Materialsmentioning

confidence: 99%

Section: Encapsulation Within Mesoporous Materialsmentioning

confidence: 99%

New Strategies for the Preparation of Sinter‐Resistant Metal‐Nanoparticle‐Based Catalysts

et al. 2019

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201901905. Supported metal nanoparticles are widely used as catalysts in the industrial production of chemicals, but still suffer from deactivation because of metal leaching and sintering at high temperature. In recent years, serious efforts have been devoted to developing new strategies for stabilizing metal nanoparticles. Recent developments for preparing sinter-resistant metalnanoparticle catalysts via strong metal-support interactions, encapsulation with oxide or carbon layers and within mesoporous materials, and fixation in zeolite crystals, are briefly summarized. Furthermore, the current challenges and future perspectives for the preparation of highly efficient and extraordinarily stable metal-nanoparticle-based catalysts, and suggestions regarding the mechanisms involved in sinter resistance, are proposed. Nanoparticle Catalysts

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“…Fuel cells are attractive power supplies for versatile applications of hydrogen. In general, hydrogen is obtained by the steam reforming of methane 18 ; recently, renewable oxygenated hydrocarbons such as methanol, ethanol, dimethyl ether (DME), and glycerol have also been used 19,20 . CO 2 methanation 21,22 and oxidative dehydrogenation of ethane using CO 2 23 are promising routes for converting CO 2 into fuels and chemicals toward CO 2 emission control.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Mesoporous Silica by Nonionic Surfactant Micelle–Templated Gelation of Na2SiO3 and H2SiF6 and Application as a Catalyst Carrier for the Partial Oxidation of CH4

Park

Kim

Seo

et al. 2019

Sci Rep

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Mesoporous silica (MSPN12) was prepared by nonionic surfactant micelle–templated gelation of sodium silicate (Na2SiO3) and fluorosilicic acid (H2SiF6) in aqueous solution, characterized by a range of instrumental techniques, and tested as a support for Ni and Rh catalysts in the partial oxidation of methane (POM). Calcined and sintered MSPN12 exhibited well-defined d00l-spacings (3.5–4.39 nm), narrow pore distributions (2.4–3.1 nm), and large specific surface areas (552–1,246 m2 g−1), and was found to be highly thermally stable. Microscopic imaging revealed that MSPN12 comprised spherical particles with a uniform diameter of ~0.7 µm, with each particle featuring firm and regular honeycomb-type pores. MSPN12-loaded Ni and Rh maintained stable POM activity at 700 °C during almost 100 h on stream, which were comparable to those for the commercial Rh(5)/Al2O3 catalyst in terms of methane conversion and H2 formation selectivity. Thus, the combination of structural stability and favorable physicochemical properties resulted in good POM performance.

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Achieving efficient and robust catalytic reforming on dual-sites of Cu species

Abstract: This paper describes how Cu+ species act as electrophilic sites to facilitate the adsorption and activation of formate and restrict the Ostwald ripening of Cu species, leading to an efficient and robust steam reforming of bio-DME.

Cited by 76 publications

References 44 publications

Identification of intrinsic active sites in ternary CuZnTi catalysts toward low-temperature water gas shift reaction

Identification of intrinsic active sites in ternary CuZnTi catalysts toward low-temperature water gas shift reaction

New Strategies for the Preparation of Sinter‐Resistant Metal‐Nanoparticle‐Based Catalysts

Preparation of Mesoporous Silica by Nonionic Surfactant Micelle–Templated Gelation of Na2SiO3 and H2SiF6 and Application as a Catalyst Carrier for the Partial Oxidation of CH4

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