Acetylene Semihydrogenation over Pd–Bi Intermetallic Compounds: A DFT Combined with Microkinetic Modeling Study DOI
Bingbing Li,

Hong-Yan Ma,

Gui‐Chang Wang

et al.

Langmuir, Journal Year: 2024, Volume and Issue: 40(36), P. 19043 - 19050

Published: Aug. 28, 2024

Acetylene semihydrogenation is an important process both theoretically and experimentally. Pure Pd catalysts usually suffer from limited selectivity for ethylene products poor stability. Pd–Bi bimetallic compounds are synthesized show not only excellent catalytic performance but also remarkable long-term However, the detailed mechanism still unclear. In this paper, acetylene on Pd(100), Pd3Bi1(100), Pd1Bi1(100) studied by density functional theory (DFT) calculation microkinetic modeling. Adding Bi causes surface d-band center (εd) to move a lower energy, adsorption strength of intermediate becomes weaker. Besides, ethylidyne (CCH3) formation more difficult alloy due lack continuous atoms. As spectator, CCH3 deactivates alloys steric effect. high because weakly bonded ethylene. We found relationship between εd catalysts' activity selectivity. This study may supply some clues design selective hydrogenation catalysts.

Language: Английский

Atomic-Level Asymmetric Tuning of the Co1–N3P1 Catalyst for Highly Efficient N-Alkylation of Amines with Alcohols DOI
Huan Liu, Luyao Tian, Zhentao Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20518 - 20529

Published: July 12, 2024

Despite the extensive development of non-noble metals for

Language: Английский

Citations

15
Do we achieve “1 + 1 > 2” in dual-atom or dual-single-atom catalysts? DOI
Xue Yang,

Linyao Xu,

Yuxin Li

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 516, P. 215961 - 215961

Published: May 29, 2024

Language: Английский

Citations

12
Atomically integration of O-bridged Co-Fe hetero-pairs as tandem photocatalyst towards highly efficient hydroxyl radicals production DOI

Yali Luo,

Yang Deng, Pengfei Li

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 356, P. 124255 - 124255

Published: May 31, 2024

Language: Английский

Citations

12
Encapsulation of Pd Single-Atom Sites in Zeolite for Highly Efficient Semihydrogenation of Alkynes DOI
Huan Liu, Jialu Li, Liang Xiao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(34), P. 24033 - 24041

Published: Aug. 15, 2024

Palladium (Pd)-based single-atom catalysts (SACs) have shown outstanding selectivity for semihydrogenation of alkynes, but most Pd single sites coordinated with highly electronegative atoms (such as N, O, and S) supports will result in a decrease the electron density sites, thereby weakening adsorption reactants reducing catalytic performance. Constructing rich outer-shell environment by changing coordination structure offers novel opportunity to enhance efficiency excellent alkene selectivity. Therefore, this work, we first propose situ preparation isolated encapsulated within Al/Si-rich ZSM-5 using one-pot seed-assisted growth method.

Language: Английский

Citations

12
Heteroatoms‐Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation DOI
Risheng Bai,

Guangyuan He,

Junyan Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 29, 2024

As a fundamental industrial catalytic process, the semihydrogenation of alkynes presents challenge in striking balance between activity and selectivity due to issue over-hydrogenation. Herein, we develop an efficient system based on single-atom Pd catalysts supported boron-containing amorphous zeolites (Pd/AZ-B), achieving tradeoff breaking for selective hydrogenation alkynes. Advanced characterizations theoretical density functional theory calculations confirm that incorporated B atoms Pd/AZ-B can not only alter geometric electronic properties by controlling electron migration from but also mitigate interaction alkene catalyst supports. This boosts exceptional efficacy phenylacetylene styrene under mild conditions (298 K, 2 bar H

Language: Английский

Citations

10
Self‐assembled Gap‐Rich PdMn Nanofibers with High Mass/Electron Transport Highways for Electrocatalytic Reforming of Waste Plastics DOI Open Access

Songliang Liu,

Kun Ma,

Huaifang Teng

et al.

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Innovating nanocatalysts with both high intrinsic catalytic activity and selectivity is crucial for multi‐electron reactions, however, their low mass/electron transport at industrial‐level currents often overlooked, which usually leads to comprehensive performance the device level. Herein, a Cl − /O 2 etching‐assisted self‐assembly strategy reported synthesizing self‐assembled gap‐rich PdMn nanofibers highway greatly enhancing electrocatalytic reforming of waste plastics currents. The nanofiber shows excellent in upcycling into glycolic acid, current density 223 mA cm −2 @0.75 V ( vs RHE), (95.6%), Faraday efficiency (94.3%) acid flow electrolyzer. Density functional theory calculation, X‐ray absorption spectroscopy combined situ electrochemical Fourier transform infrared reveals that introduction highly oxophilic Mn induces downshift d ‐band center Pd, optimizes adsorption energy reaction intermediates on surface, thereby facilitating desorption as high‐value product. Computational fluid dynamics simulations confirm structure conducive mass transfer deliver an current.

Language: Английский

Citations

2
Building Asymmetric Zn–N3 Bridge between 2D Photocatalyst and Co‐catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis DOI
Weikang Wang, Rong Liu, Jianjun Zhang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 8, 2024

Abstract Two‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane recombination and thus improved quantum efficiency. Although some strategies, such as π–π stacking van der Waals interaction, have been developed so far, directed still cannot be achieved. Herein, we report strategy forming asymmetric Zn−N 3 units that can bridge nitrogen (N)‐doped carbon layers with nitride nanosheets (C N 4 −Zn−N(C)) address this challenge. The symmetry‐breaking moiety, which has an local distribution, enables interfacial between the C photocatalyst N‐doped co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, separation significantly enhanced bonding bridges. result, designed −Zn−N(C) catalyst exhibits dramatically H 2 O photosynthesis activity, outperforming most reported ‐based catalysts. This work highlights importance tailoring chemical channels in photocatalysts at molecular level achieve effective spatial separation.

Language: Английский

Citations

8
Regulating Second-Shell Coordination in Cobalt Single-Atom Catalysts toward Highly Selective Hydrogenation DOI

Yunxia Duan,

Yongming Xia,

Yuxuan Ling

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(32), P. 21326 - 21335

Published: July 31, 2024

Manipulating the local coordination environment of central metal atoms in single-atom catalysts (SACs) is a powerful strategy to exploit efficient SACs with optimal electronic structures for various applications. Herein, Co-SACs featured by Co single coordinating S second shell dispersed nitrogen-doped carbon matrix have been developed toward selective hydrogenation halo-nitrobenzene. The location atom model Co-SAC verified through synchrotron-based X-ray absorption spectroscopy and theoretical calculations. resultant containing second-coordination demonstrate excellent activity outstanding durability hydrogenation, superior most precious metal-based catalysts. In situ characterizations results verify that high selectivity are attributed advantageous formation Co–O bond between p-chloronitrobenzene at Co1N4–S moieties lower free energy barriers reaction. Our findings unveil correlation performance second-shell SACs.

Language: Английский

Citations

7
Zr(OH)4‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr‐O‐H as Active Site: Inactive for Free Styrene DOI

Wenxiang Wu,

Na Li,

Chunxia Che

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 24, 2024

Abstract In the field of industrial semi‐hydrogenation trace alkynes amidst alkene feedstocks, pivotal challenge lies in circumventing hydrogenation alkenes. Herein, we present Zr(OH) 4 as an innovative catalyst for phenylacetylene, demonstrating remarkable selectivity towards styrene (>96 %), while exhibiting inactivity free styrene. Notably, achieves a 95 % conversion quasi‐industry 1 mol phenylacetylene within styrene, with mere 0.44 loss. Experimental and theoretical results confirm both terminal Zr−O−H bridge can dissociate H 2 , plays crucial role on activating through sequential process C 6 5 C≡CH→C C=CH →C CH=CH . The high rate removal is attributed to its strong adsorption capacity, has significantly weaker capacity

Language: Английский

Citations

6
Dynamically Precise Constructing Dual‐Atom Pd2 Catalyst:A Monodisperse Catalyst With High Stability for Semi‐Hydrogenation of Alkyne DOI Open Access
Yapei Yun,

Honglei Shen,

Yanan Shi

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 9, 2024

Dual-atom catalysts (DACs) originate unprecedented reactivity and maximize resource efficiency. The fundamental difficulty lies in the high complexity instability of DACs, making rational design targeted performance optimization a grand challenge. Here, an atomically dispersed Pd

Language: Английский

Citations

5