Few-Atomic Zero-Valent Palladium Ensembles for Efficient Reductive Dehydrogenation and Dehalogenation Catalysis

Li, Zhenjie; Guo, Zhongyuan; Wu, Xinyue; Jiang, Xunheng; Li, Hao; Xu, Jiang; Yang, Kun; Lin, Daohui

doi:10.1021/acsnano.3c07724

“…Specifically, a single peak centered at 2100–2180 cm –1 is observed in the FTIR spectrum of Pd/Co 3 O 4 -0.2%, consistent with previous reports on the IR feature of CO chemisorbed on single-atom Pd sites, particularly cationic Pd species anchored onto a metal oxide support . When the Pd loading in Pd/Co 3 O 4 increases to 0.5%, this IR band becomes broader, maintaining the band center at 2140 cm –1 , and an additional shoulder at 1950–2050 cm –1 is observed, indicating the presence of chemisorbed CO with a bridge configuration. , This is consistent with Cs-HAADF-STEM results, which showed a transition in the structure of Pd species from single-atom sites to Pd ensembles, promoting the bridged adsorption of CO by providing contiguous Pd sites . Of note is, compared with the literature-reported value, the IR bands of the atop- and bridged-adsorbed CO showed an evident blue shift .…”

Section: Resultssupporting

confidence: 90%

Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Du,

Ran,

Zhao

et al. 2024

ACS EST Eng.

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The complete detoxification of hazardous organic pollutants is crucial for water treatment. However, this often requires the cooperation of multiple treatment processes catalyzed by different catalysts, leading to a complex water treatment infrastructure design and high operational costs. To address this challenge, we developed fully exposed palladium (Pd) ensemble (Pd n )-loaded ultrathin Co 3 O 4 nanosheets (NSs) (Pd n /Co 3 O 4 NSs) as a reductive−oxidative dual-active catalyst for the efficient detoxification of halogenated organic pollutants. During the treatment of simulated water contaminated by 4-chlorophenol (4-CP), a representative persistent organic pollutant, Pd n reactive centers rapidly hydrodechlorinate 4-CP into low-toxicity phenol with activity ≥10 times that of benchmark catalysts. The synergy between the Pd ensembles and oxygen vacancies further promotes the rapid and selective hydrogenation of phenol into cyclohexanone on Co 3 O 4 NSs. Subsequently, cyclohexanone is oxidized by peroxymonosulfate (PMS) under Co 3 O 4 activation. A cell assay-based toxicity study confirmed that stimulated polluted environmental water is fully detoxified after treatment with the designed Pd n /Co 3 O 4 NSs catalyst. This study provides new insights into the rational design of Pd catalysts for the catalytic removal of persistent organic pollutants, particularly halogenated aromatics, paving the way for facile, low-cost, and highly efficient water treatment processes.

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Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm

Guo,

Yu,

Li

et al. 2024

Angewandte Chemie

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Authentic surface structures under reaction conditions determine the activity and selectivity of electrocatalysts, therefore, the knowledge of the structure−activity relationship can facilitate the design of efficient catalyst structures for specific reactivity requirements. However, understanding the relationship between a more realistic active surface and its performance is challenging due to the complicated interface microenvironment in electrocatalysis. Herein, we proposed a standard research paradigm to effectively decipher the structure−activity relationship in electrocatalysis, which is exemplified in the CO2 electroreduction over SnO2. The proposed practice has aided in discovering authentic/resting surface states (Sn layer) of SnO2 accountable for the electrochemical CO2 reduction reaction (CO2RR) performance under electrocatalytic conditions, which then is corroborated in the subsequent CO2RR experiments over SnO2 with different morphologies (nanorods, nanoparticles, and nanosheets) in combination with in−situ characterizations. This proposed methodology is further extended to the SnO electrocatalysts, providing helpful insights into catalytic structures. It is believed that our proposed standard research paradigm is also applicable to other electrocatalytic systems, in the meantime, decreases the discrepancy between theory and experiments, and accelerates the design of catalyst structures that achieve sustainable performance for energy conversion.

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Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm

Guo,

Yu,

Li

et al. 2024

Angew Chem Int Ed

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24

0

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Authentic surface structures under reaction conditions determine the activity and selectivity of electrocatalysts, therefore, the knowledge of the structure−activity relationship can facilitate the design of efficient catalyst structures for specific reactivity requirements. However, understanding the relationship between a more realistic active surface and its performance is challenging due to the complicated interface microenvironment in electrocatalysis. Herein, we proposed a standard research paradigm to effectively decipher the structure−activity relationship in electrocatalysis, which is exemplified in the CO2 electroreduction over SnO2. The proposed practice has aided in discovering authentic/resting surface states (Sn layer) of SnO2 accountable for the electrochemical CO2 reduction reaction (CO2RR) performance under electrocatalytic conditions, which then is corroborated in the subsequent CO2RR experiments over SnO2 with different morphologies (nanorods, nanoparticles, and nanosheets) in combination with in−situ characterizations. This proposed methodology is further extended to the SnO electrocatalysts, providing helpful insights into catalytic structures. It is believed that our proposed standard research paradigm is also applicable to other electrocatalytic systems, in the meantime, decreases the discrepancy between theory and experiments, and accelerates the design of catalyst structures that achieve sustainable performance for energy conversion.

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Few-Atomic Zero-Valent Palladium Ensembles for Efficient Reductive Dehydrogenation and Dehalogenation Catalysis

Cited by 9 publications

References 67 publications

Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm

Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm

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Few-Atomic Zero-Valent Palladium Ensembles for Efficient Reductive Dehydrogenation and Dehalogenation Catalysis

Cited by 9 publications

References 67 publications

Fully Exposed Pd Ensembles on Ultrathin Co3O4 Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Fully Exposed Pd Ensembles on Ultrathin Co3O4 Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Deciphering Structure‐Activity Relationship Towards CO2 Electroreduction over SnO2 by A Standard Research Paradigm

Deciphering Structure‐Activity Relationship Towards CO2 Electroreduction over SnO2 by A Standard Research Paradigm

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Product

Resources

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Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm

Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm