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Anchoring Pt Single Atoms on Te Nanowires for Plasmon-Enhanced Dehydrogenation of Formic Acid at Room Temperature.

ABSTRACT: Formic acid (HCOOH), as a promising hydrogen carrier, is renewable, safe, and nontoxic. However, the catalytic dehydrogenation of HCOOH is typically conducted at elevated temperature. Here, HCOOH decomposition is successfully achieved for hydrogen production on the developed Pt single atoms modified Te nanowires with the Pt mass loading of 1.1% (1.1%Pt/Te) at room temperature via a plasmon-enhanced catalytic process. Impressively, 1.1%Pt/Te delivers 100% selectivity for hydrogen and the highest turnover frequency number of 3070 h^-1 at 25 °C, which is significantly higher than that of Pt single atoms and Pt nanoclusters coloaded Te nanowires, Pt nanocrystals decorated Te nanowires, and commercial Pt/C. A plasmonic hot-electron driven mechanism rather than photothermal effect domains the enhancement of catalytic activity for 1.1%Pt/Te under light. The transformation of HCOO* to CO₂ ^δ ^-* on Pt atoms is proved to be the rate-determining step by further mechanistic studies. 1.1%Pt/Te exhibits tremendous catalytic activity toward the decomposition of HCOOH owing to its plasmonic hot-electron driven mechanism, which efficiently stimulates the rate-determining step. In addition, hot electrons generated by the Te atoms nearby Pt single atoms are regarded to directly inject into the reactants adsorbed and activated on Pt single atoms.

SUBMITTER: Han L

PROVIDER: S-EPMC6662073 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Anchoring Pt Single Atoms on Te Nanowires for Plasmon-Enhanced Dehydrogenation of Formic Acid at Room Temperature.

Han Lei L Zhang Leijie L Wu Hong H Zu Hualu H Cui Peixin P Guo Jiasheng J Guo Ruihan R Ye Jian J Zhu Junfa J Zheng Xusheng X Yang Liuqing L Zhong Yici Y Liang Shuquan S Wang Liangbing L

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20190417 12

Formic acid (HCOOH), as a promising hydrogen carrier, is renewable, safe, and nontoxic. However, the catalytic dehydrogenation of HCOOH is typically conducted at elevated temperature. Here, HCOOH decomposition is successfully achieved for hydrogen production on the developed Pt single atoms modified Te nanowires with the Pt mass loading of 1.1% (1.1%Pt/Te) at room temperature via a plasmon-enhanced catalytic process. Impressively, 1.1%Pt/Te delivers 100% selectivity for hydrogen and the highest ...[more]

PMID: 31380161

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Project description:The non-oxidative catalytic dehydrogenation of light alkanes via C-H activation is a highly endothermic process that generally requires high temperatures and/or a sacrificial hydrogen acceptor to overcome unfavorable thermodynamics. This is complicated by alkanes being such poor ligands, meaning that binding at metal centers prior to C-H activation is disfavored. We demonstrate that by biasing the pre-equilibrium of alkane binding, by using solid-state molecular organometallic chemistry (SMOM-chem), well-defined isobutane and cyclohexane σ-complexes, [Rh(Cy2PCH2CH2PCy2)(η:η-(H3C)CH(CH3)2][BArF4] and [Rh(Cy2PCH2CH2PCy2)(η:η-C6H12)][BArF4] can be prepared by simple hydrogenation in a solid/gas single-crystal to single-crystal transformation of precursor alkene complexes. Solid-gas H/D exchange with D2 occurs at all C-H bonds in both alkane complexes, pointing to a variety of low energy fluxional processes that occur for the bound alkane ligands in the solid-state. These are probed by variable temperature solid-state nuclear magnetic resonance experiments and periodic density functional theory (DFT) calculations. These alkane σ-complexes undergo spontaneous acceptorless dehydrogenation at 298 K to reform the corresponding isobutene and cyclohexadiene complexes, by simple application of vacuum or Ar-flow to remove H2. These processes can be followed temporally, and modeled using classical chemical, or Johnson-Mehl-Avrami-Kologoromov, kinetics. When per-deuteration is coupled with dehydrogenation of cyclohexane to cyclohexadiene, this allows for two successive KIEs to be determined [kH/kD = 3.6(5) and 10.8(6)], showing that the rate-determining steps involve C-H activation. Periodic DFT calculations predict overall barriers of 20.6 and 24.4 kcal/mol for the two dehydrogenation steps, in good agreement with the values determined experimentally. The calculations also identify significant C-H bond elongation in both rate-limiting transition states and suggest that the large kH/kD for the second dehydrogenation results from a pre-equilibrium involving C-H oxidative cleavage and a subsequent rate-limiting β-H transfer step.

Dataset Information

Anchoring Pt Single Atoms on Te Nanowires for Plasmon-Enhanced Dehydrogenation of Formic Acid at Room Temperature.

Publications

Anchoring Pt Single Atoms on Te Nanowires for Plasmon-Enhanced Dehydrogenation of Formic Acid at Room Temperature.

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