Electrothermal Water‐Gas Shift Reaction at Room Temperature with a Silicomolybdate‐Based Palladium Single‐Atom Catalyst

Chang, Jinquan; Hülsey, Max J.; Wang, Sikai; Li, Maoshuai; Ma, Xinbin; Yan, Ning

doi:10.1002/anie.202218265

Cited by 19 publications

(5 citation statements)

References 67 publications

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“…As observed in Figure 3b, the FT k3‐weighted EXAFS spectra data of fresh and used Pd/ϵ‐PANI exhibit a characteristic peak at 1.4 Å that is assigned to Pd−N/C coordination. The prominent peak centered at 2.48 Å of Pd foil is attributed to Pd−Pd coordination [26] . Based on this, no obvious metallic Pd−Pd peaks are observed in the Pd/ϵ‐PANI catalysts, implying the atomic dispersion of the Pd species.…”

Section: Resultsmentioning

confidence: 80%

“…The prominent peak centered at 2.48 Å of Pd foil is attributed to PdÀ Pd coordination. [26] Based on this, no obvious metallic PdÀ Pd peaks are observed in the Pd/ɛ-PANI catalysts, implying the atomic dispersion of the Pd species. The Pd coordination numbers of fresh and used Pd/ɛ-PANI samples, determined by quantitative EXAFS fitting (Figure 3d, e and Table S4), were 2.0 and 1.8, respectively, and the well-fitted spectra demonstrated a PdÀ N/C bond length of 2.04 Å.…”

Section: Angewandte Chemiementioning

confidence: 85%

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Template‐Oriented Polyaniline‐Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives

et al. 2023

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Developing well‐defined structures and desired properties for porous organic polymer (POP) supported catalysts by controlling their composition, size, and morphology is of great significance. Herein, we report a preparation of polyaniline (PANI) supported Pd nanoparticles (NPs) with controllable structure and morphology. The protocol involves the introduction of MnO2 with different crystal structures (α, β, γ, δ, ϵ) serving as both the reaction template and the oxidant. The different forms of MnO2 each convert aniline to a PANI that contains a unique regular distribution of benzene and quinone. This leads to the Pd/PANI catalysts with different charge transfer properties between Pd and PANI, as well as different dispersions of the metal NPs. In this case, the Pd/ϵ‐PANI catalyst greatly improves the turnover frequency (TOF; to 88.3 h−1), in the reductive coupling of furfural derivatives to potential bio‐based plasticizers. Systematic characterizations reveal the unique oxidation state of the support in the Pd/ϵ‐PANI catalyst and coordination mode of Pd that drives the formation of highly dispersed Pd nanoclusters. Density functional theory (DFT) calculations show the more electron rich Pd/PANI catalyst has the lower energy barrier in the oxidative addition step, which favors the C−C coupling reaction.

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Section: Resultsmentioning

confidence: 80%

Section: Angewandte Chemiementioning

confidence: 85%

Template‐Oriented Polyaniline‐Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives

et al. 2023

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“…The introduction of Cu weakens the adsorption of CO* on Pd and enhances the adsorption of OH*, thereby optimizing the performance of the catalyst. [111] What's more, Chang et al [112] reported a Pd single-atom catalyst (Pd 1 /CsSMA) supported on silicomolybdic acid (SMA), which introduced phosphomolybdic acid (PMA) as the redox medium for indirect oxidation of CO in the reaction (Figure 9b). Fortunately, this provides innovative approach to solving the problems of low solubility of CO in solution and mass transfer of reactants.…”

Section: Comentioning

confidence: 99%

Recent Advances in Hydrogen Production from Hybrid Water Electrolysis through Alternative Oxidation Reactions

Fan,

Wang,

et al. 2024

ChemCatChem

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Water splitting driven by green electricity from renewable energy input to produce H2 has been widely considered as a promising strategy to realize the goals for future clean energy. However, in conventional overall water electrolysis, the sluggish kinetics and high onset potential of anode OER limit the cathode HER rate, which lowers the overall energy conversion efficiency. Over the past decade, an innovative concept involving hybrid water electrolysis by replacing OER with thermodynamically more favorable oxidation reactions coupling with the cathodic hydrogen evolution reaction has been devised to alleviate the limitations associated with the anodic OER. In this review, we summarize the recent progress concerning electrochemical hydrogen production by coupling the oxidation of molecules incorporating hydroxyl, aldehyde, and amino functional groups, with special emphasis on alternative reactions involving CO and sulfide. Finally, the remaining challenges and future perspectives are also discussed. We hope this review will accelerate the development of novel strategies for practicable H2 production from hybrid water electrolysis.

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“…Leveraging the high activity of polyoxometalate-supported SACs for CO oxidation, we developed an electrothermal reaction system for the room-temperature water−gas shift reaction, with the thermal oxidation of CO over a Pd 1 /CsSMA single-atom catalyst and the electrocatalytic evolution of H 2 at the cathode, coupled with PMA as a redox mediator. 49 The decoupled H 2 evolution and CO oxidation in different compartments enabled H generation in high purity (99.99%) in the cathode chamber and process optimization via separated thermal and electrocatalytic reaction steps. Equipped with a well-defined and tunable catalyst system as well as techniques to study the evolution of active sites under reaction conditions, we attempted to study more fundamental phenomena in the field of heterogeneous catalysis.…”

Section: Catalysts With Ionic Liquidsmentioning

confidence: 99%

Approaching Molecular Definition on Oxide-Supported Single-Atom Catalysts

et al. 2023

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Conspectus Single-atom catalysts (SACs) offer unique advantages such as high (noble) metal utilization through maximum possible dispersion, large metal–support contact areas, and oxidation states usually unattainable in classic nanoparticle catalysis. In addition, SACs can serve as models for determining active sites, a simultaneously desired as well as elusive target in the field of heterogeneous catalysis. Due to the complexity of heterogeneous catalysts bearing a variety of different sites on metal particles and the respective support as well as at their interface, studies of intrinsic activities and selectivities remain largely inconclusive. While SACs could close this gap, many supported SACs remain intrinsically ill-defined due to complexities arising from the variety of different adsorption sites for atomically dispersed metals, hampering the establishment of meaningful structure–activity correlations. In addition to overcoming this limitation, well-defined SACs could even be utilized to shed light on fundamental phenomena in catalysis that remain ambiguous when studies are obscured by the complexity of heterogeneous catalysts. In this Account, we describe approaches to break down the complexity of supported single-atom catalysts through the careful choice of oxide supports with specific binding motives as well as the adsorption of well-defined ligands such as ionic liquids on single metal sites. An example of molecularly defined oxide supports is polyoxometalates (POMs), which are metal oxo clusters with precisely known composition and structure. POMs exhibit a limited number of sites to anchor atomically dispersed metals such as Pt, Pd, and Rh. Polyoxometalate-supported single-atom catalysts (POM-SACs) thus represent ideal systems for the in situ spectroscopic study of single atom sites during reactions as, in principle, all sites are identical and thus equally active in catalytic reactions. We have utilized this benefit in studies of the mechanism of CO and alcohol oxidation reactions as well as the hydro(deoxy)genation of various biomass-derived compounds. More so, the redox properties of polyoxometalates can be finely tuned by changing the composition of the support while keeping the geometry of the single-atom active site largely constant. We further developed soluble analogues of heterogeneous POM-SACs, opening the door to advanced liquid-phase nuclear magnetic resonance (NMR) and UV–vis techniques but, in particular, to electrospray ionization mass spectrometry (ESI-MS) which proves powerful in determining catalytic intermediates as well as their gas-phase reactivity. Employing this technique, we were able to resolve some of the long-standing questions about hydrogen spillover, demonstrating the broad utility of studies on defined model catalysts.

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Electrothermal Water‐Gas Shift Reaction at Room Temperature with a Silicomolybdate‐Based Palladium Single‐Atom Catalyst

Cited by 19 publications

References 67 publications

Template‐Oriented Polyaniline‐Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives

Template‐Oriented Polyaniline‐Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives

Recent Advances in Hydrogen Production from Hybrid Water Electrolysis through Alternative Oxidation Reactions

Approaching Molecular Definition on Oxide-Supported Single-Atom Catalysts

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