A Single‐Atom Cobalt Catalyst for the Fluorination of Acyl Chlorides at Parts‐per‐Million Catalyst Loading

Li, Wen‐Hao; Ye, Bo‐Chao; Yang, Jiarui; Wang, Ye; Yang, Chang‐Jie; Pan, Ying‐Ming; Tang, Hai‐Tao; Wang, Dingsheng; Li, Yadong

doi:10.1002/ange.202209749

Cited by 4 publications

(2 citation statements)

References 62 publications

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“…41 Oxidative fluorination of acyl chlorides could be realized at parts-per-million catalyst loading using Co 1 −N 4 @NC SAC. 42 Heterogeneous organonitrogen chemical synthesis represents another type of important transformation for valued-added chemicals, urging the development of SACs for rapid construction of N-heterocycles. 43 Nonetheless, such a single-site pathway can be problematic in balancing the catalytic activity and stability (Section 2.3).…”

Section: Multi-site Pathway Versus Single-site Pathwaymentioning

confidence: 99%

Engineering Single Atom Catalysts for Flow Production: From Catalyst Design to Reactor Understandings

Chen

Liu

2022

Acc. Mater. Res.

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Conspectus In heterogeneous catalysis, the long-standing challenge is to achieve extremely high activity and chemoselectivity in liquid-phase organic transformations comparable to that of homogeneous or enzymatic processes. Single-atom catalysts (SACs) with atomically precise coordination are developed with the objectives to mimic the homogeneous pathways but face stability issues due to metal leaching or clustering. Additionally, the practical application of SACs in chemical production is hampered by the lack of standard preparation protocols and low conversion using laboratory batch reactors. This Account focuses on our recent studies in both catalyst design and reactor-level engineering for the flow synthesis of fine chemicals via SACs. At the catalyst and reaction level, we will discuss the intrinsic mechanism that controls reactivity and chemoselectivity in the SAC-catalyzed process and highlight examples where SACs outperform other catalytic approaches. Specifically, we reported the SAC-mediated preparation and late-stage functionalization of pharmaceutical drugs, including lonidamine, Tamiflu, cavosonstat, indomethacin, and many others by chemoselective transformations in a sequential or multicomponent manner. The ability of ultrahigh loading SACs in providing a multisite pathway for organic transformations involving two or more reactants is highlighted and contrasted with the single-site pathway in conventional SACs. Molecular-level understanding on the dynamic catalytic cycle obtained using operando X-ray absorption spectroscopies provides guidance for the design of more effective and leach resistant SACs. This also calls for the transformation of laboratory powder-based catalysts into industrially viable monolithic catalysts via formulation to further enhance the leach resistance. At the reactor level, we will highlight the importance of continuous-flow techniques in maximizing productivity and simplifying process transfer from laboratory to commercial production. Particularly, we discuss the use of fuel cell-type flow stacks for quantitative production of fine chemicals, including the synthesis of multifunctional anilines at a 5.8 g h–1 productivity using a Pt SAC module (3.2 mg Pt). Insight into multiscale reactor processes, for instance, the fluid diffusion kinetics, heat transfer, and influence of porosity and the gas–liquid–solid interface are provided by computational fluidic dynamics calculations as well as experimental techniques. In many cases, catalytic processes are more limited by mass diffusion than the intrinsic activity of the catalyst, calling for process optimization and engineering at the reactor level to enhance the productivity. Finally, we also identify technical barriers that need to be overcome in SAC research and offer our perspective on standardized and scalable protocols for mass production, the production cost analysis of typical SACs, high-throughput screening platforms, and novel flow reactor designs involving photochemical and electrochemical reactions for up-scaling chemic...

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Section: Multi-site Pathway Versus Single-site Pathwaymentioning

confidence: 99%

Engineering Single Atom Catalysts for Flow Production: From Catalyst Design to Reactor Understandings

Chen

Liu

2022

Acc. Mater. Res.

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“…The chemists synthesized the catalysts downsizing from the bulk to the nanomaterial, and finally to the atomic active sites nowadays. [19][20][21][22] In this process, the understanding of the underlying mechanism became more systematic, and the catalysts with higher catalytic efficiency were designed.…”

Section: Introductionmentioning

confidence: 99%

Single‐atom materials: The application in energy conversion

Zhu,

Yang,

Zhang

et al. 2024

Interdisciplinary Materials

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Single‐atom materials (SAMs) have become one of the most important power sources to push the field of energy conversion forward. Among the main types of energy, including thermal energy, electrical energy, solar energy, and biomass energy, SAMs have realized ultra‐high efficiency and show an appealing future in practical application. More than high activity, the uniform active sites also provide a convincible model for chemists to design and comprehend the mechanism behind the phenomenon. Therefore, we presented an insightful review of the application of the single‐atom material in the field of energy conversion. The challenges (e.g., accurate synthesis and practical application) and future directions (e.g., machine learning and efficient design) of the applications of SAMs in energy conversion are included, aiming to provide guidance for the research in the next step.

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A “Pre‐Division Metal Clusters” Strategy to Mediate Efficient Dual‐Active Sites ORR Catalyst for Ultralong Rechargeable Zn‐Air Battery

Zhao

Wen

et al. 2023

Angewandte Chemie

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To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal‐air batteries, catalysts with dual‐active centers have stood out. Here, a “pre‐division metal clusters” strategy is firstly conceived to fabricate a N,S‐dual doped honeycomb‐like carbon matrix inlaid with CoN4 sites and wrapped Co2P nanoclusters as dual‐active centers (Co2P/CoN4@NSC‐500). A crystalline {CoII2} coordination cluster divided by periphery second organic layers is well‐designed to realize delocalized dispersion before calcination. The optimal Co2P/CoN4@NSC‐500 executes excellent 4e− ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn‐air battery (ZAB) assembled by Co2P/CoN4@NSC‐500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm−2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.

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A Single‐Atom Cobalt Catalyst for the Fluorination of Acyl Chlorides at Parts‐per‐Million Catalyst Loading

Cited by 4 publications

References 62 publications

Engineering Single Atom Catalysts for Flow Production: From Catalyst Design to Reactor Understandings

Engineering Single Atom Catalysts for Flow Production: From Catalyst Design to Reactor Understandings

Single‐atom materials: The application in energy conversion

A “Pre‐Division Metal Clusters” Strategy to Mediate Efficient Dual‐Active Sites ORR Catalyst for Ultralong Rechargeable Zn‐Air Battery

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