Trace Pt atoms as electronic promoters in Pd clusters for direct synthesis of hydrogen peroxide

Zhang, Ying; Sun, Qingdi; Guo, Guanghui; Cheng, Yuanbing; Zhang, Xingcong; Ji, Hongbing; He, Xiaohui

doi:10.1016/j.cej.2022.138867

Cited by 19 publications

(21 citation statements)

References 45 publications

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“…In this work, the content of Co–N x active sites increases upon the increase of Au addition, and we believe that this is because that the Au component addition can change the Co coordination environment and promote the dispersion of Co atoms. A similar result was also observed in the Pt single atom (SA)-modified Pd cluster catalyst, and it was found that the addition of trace amounts of Pt SAs in fully exposed Pd clusters could reduce the coordination numbers of Pd–O and Pd–Pd shells, indicating that the addition of trace Pt SAs could change the coordination environment of Pd atoms . In addition, the binding energy of Co–N x in Au 0.05 Co@NC shows the largest negative shift of 0.5 eV compared with that of Co@NC, and this may be caused by Au doping, indicating an electronic rich state of Co–N x species over the Au 0.05 Co@NC catalyst.…”

Section: Resultssupporting

confidence: 67%

Regulation of the Co–N_x Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Wang

Zhang

et al. 2022

ACS Catal.

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The Co–N x active sites play a critical role over the Co@NC catalyst in the heterogeneous catalysis. However, the effective methods for the regulation of the content and electronic structure of Co–N x active sites to enhance the catalytic efficiency of heterogeneous catalysts are still insufficient. Herein, a nitrogen-doped porous carbon-encapsulated Au-doped Co nanoparticle catalysts with abundant and electron-rich Co–N x sites in the outer carbon layer was designed by a Au doping strategy through pyrolysis of the HAuCl4-modified ZIF-67 metal organic framework precursor. The optimal catalyst exhibits improved catalytic performance in alcohol selective oxidative esterification. The linear relationship between the ester yield and Co–N x species content, combined with a series of control experiments, indicated that the Co–N x active sites are crucial for achieving the excellent catalytic activity (yield: 99.9%). In situ diffuse reflectance infrared Fourier transform spectroscopy, O2-temperature-programed desorption characterizations, active oxygen species quenching experiments together with density functional theory calculations results indicate that Au doping in the Co nanoparticle core increases the content and the electron density of Co–N x species on the outer carbon shell, which enhanced the chemical adsorption and activation of molecular O2 for producing reactive O2 •– species. This study demonstrated a novel Co–N x active site regulation strategy for the efficient selective oxidative esterification of alcohols under mild reaction conditions.

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Section: Resultssupporting

confidence: 67%

Regulation of the Co–N_x Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Wang

Zhang

et al. 2022

ACS Catal.

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“…Two peaks at 2122 and 1932 cm –1 of Pd 1 /Al 2 O 3 are attributed to linearly adsorbed CO on low-coordinated Pd atoms and bridged adsorbed CO on Pd atoms, respectively . However, for Pd 1 Ba 1 /Al 2 O 3 , the linearly adsorbed and bridged adsorbed CO were shifted to 2117 and 1923 cm –1 , respectively, indicating the fact that there was a red shift toward a lower wavenumber, which was due to the increased d-orbital electron density caused by charge transfer from Ba to Pd atoms Figure b and Figure S9a show the Pd 3d and Ba 3d spectra of catalysts, respectively, and Figure S9b shows the XPS full spectra.…”

mentioning

confidence: 95%

“…Recently, the concept of metallic SAs as promoters to modify the electronic structure of active sites has been proposed. ,− For example, He and co-workers prepared fully exposed Pd clusters with Pt SAs as electronic promoters for direct synthesis of hydrogen peroxide . The presence of Pt atoms favored the electron transfer to form an electron-rich Pd species, which greatly improved the hydrogen peroxide productivity and selectivity.…”

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confidence: 99%

“…16,25−27 For example, He and co-workers prepared fully exposed Pd clusters with Pt SAs as electronic promoters for direct synthesis of hydrogen peroxide. 28 The presence of Pt atoms favored the electron transfer to form an electron-rich Pd species, which greatly improved the hydrogen peroxide productivity and selectivity. Therefore, it is promising to construct electron-rich atomically dispersed sites, which should facilitate H 2 dissociation and improve the activities toward hydrogenation.…”

mentioning

confidence: 99%

“…35 However, for Pd 1 Ba 1 /Al 2 O 3 , the linearly adsorbed and bridged adsorbed CO were shifted to 2117 and 1923 cm −1 , respectively, indicating the fact that there was a red shift toward a lower wavenumber, which was due to the increased d-orbital electron density caused by charge transfer from Ba to Pd atoms. 28 Figure 2b and Figure S9a show the Pd 3d and Ba 3d spectra of catalysts, respectively, and Figure S9b shows the XPS full spectra. The intense peaks at 342.4 and 337.1 eV in the Pd 3d XPS spectra of Pd 1 /Al 2 O 3 were ascribed to Pd 2+ 3d 3/2 and Pd 2+ 3d 5/2 , respectively.…”

mentioning

confidence: 99%

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Enhanced Hydrogenation Properties of Pd Single Atom Catalysts with Atomically Dispersed Ba Sites as Electronic Promoters

et al. 2022

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Precise adjustment of the electronic structure of heterogeneous catalysts is an effective strategy to improve their catalytic properties. By preparing Pd1Ba1/Al2O3 double atom catalysts with a ball milling method as a model catalyst, we demonstrate an interfacial electronic effect of Pd species induced by Ba single atoms (SAs) as electronic promoters. The introduction of Ba SAs promotes the transfer of electrons from Ba atoms to Pd atoms, forming electron-rich Pdδ+ species. During catalysis, Pd species with the modification of Ba SAs lower apparent activation energy and promote H2 dissociation, which dramatically enhances the catalytic properties in several typical hydrogenation reactions under mild conditions.

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Propane dehydrogenation on Ir single‐atom catalyst modified by atomically dispersed Sn promoters in silicalite‐1 zeolite

Zhang,

Shi,

Wang

et al. 2024

AIChE Journal

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Propylene serves as a crucial feedstock for a wide range of industries engaged in the production of diverse petrochemical products. Propane dehydrogenation, an appealing technology aimed at supplanting conventional methodologies, confronts significant hurdles attributable to coke deposition and sintering in Pt‐based catalysts. Here, we report an Ir single atom encapsulated in silicalite‐1 zeolite modified with Sn single atoms as electronic promoters, displaying remarkable activity and stability, which is significantly greater than the previously reported Ir‐based catalysts and comparable to the majority of Pt‐based catalysts under similar industrial conditions (600°C, C3H8/H2 = 2/1). Spectroscopies results reveal that the introduction of Sn atoms promotes the transfer of electrons from Sn atoms to Ir atoms, forming electron‐rich Irδ+ species. DFT calculations show that the unique electronic structure lowers the energy barrier for two‐step dehydrogenation as well as favors the adsorption of propane and desorption of propylene, thus enhancing the activity and stability.

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Trace Pt atoms as electronic promoters in Pd clusters for direct synthesis of hydrogen peroxide

Cited by 19 publications

References 45 publications

Regulation of the Co–N_x Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Regulation of the Co–N_x Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Enhanced Hydrogenation Properties of Pd Single Atom Catalysts with Atomically Dispersed Ba Sites as Electronic Promoters

Propane dehydrogenation on Ir single‐atom catalyst modified by atomically dispersed Sn promoters in silicalite‐1 zeolite

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Trace Pt atoms as electronic promoters in Pd clusters for direct synthesis of hydrogen peroxide

Cited by 19 publications

References 45 publications

Regulation of the Co–Nx Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Regulation of the Co–Nx Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Enhanced Hydrogenation Properties of Pd Single Atom Catalysts with Atomically Dispersed Ba Sites as Electronic Promoters

Propane dehydrogenation on Ir single‐atom catalyst modified by atomically dispersed Sn promoters in silicalite‐1 zeolite

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Regulation of the Co–N_x Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols

Regulation of the Co–N_x Active Sites of MOF-Templated Co@NC Catalysts via Au Doping for Boosting Oxidative Esterification of Alcohols