Steering single-site metallaphotocatalytic pathway by accumulated electron on carbon nitride support

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2023-12-21 DOI:10.1016/j.apcatb.2023.123653

Bangrong Ming , Tongtong Jia , Yufan Zhang , Jikun Li , Chuncheng Chen , Wenjing Song , Jincai Zhao

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Abstract

Organic halide transformation is of high importance for fine chemical synthesis and environmental remediation. Integrated photocatalytic platforms open up distinctive reaction pathway for carbon-halogen bond activation/reconstruction. Herein we reveal carbon nitride (CN)-ligated single atom nickel (Ni₁/CN), with accumulated electron on the CN, paves Ni-mediated electron-proton transfer, enabling hydrodehalogenation, along with the catalytic carbon–oxygen (C–O) coupling. The preference for hydrodehalogenation positively correlates with density of electron on CN. EPR measurements suggest photo-generated Ni^I interacts with aryl halides, followed by electron transfer or reductive elimination to give different products. Further kinetic studies on hydrodehalogenation/C–O coupling show the reaction orders of 0.1/0.5 in aryl halide and 1.5/0.03 in (CN) electron, unveiling rate-determining step as oxidative addition to Ni^I and (CN) electron transfer for the two conversions. Our work advances in modulating aryl halide conversion by carrier accumulation on the photoactive support and guides metallaphotocatalytic platform design/operation toward target transformations.

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通过氮化碳支持物上的累积电子引导单点金属光催化途径

有机卤化物转化对精细化学品合成和环境修复具有重要意义。集成光催化平台为碳-卤键的活化/重构开辟了独特的反应途径。在此，我们揭示了氮化碳（CN）与单原子镍（Ni1/CN）的配位，在 CN 上积累的电子促进了镍介导的电子-质子转移，实现了氢脱卤以及催化碳-氧（C-O）耦合。氢化脱卤的偏好与 CN 上的电子密度成正相关。EPR 测量表明，光生成的 NiI 与芳基卤化物相互作用，然后通过电子转移或还原消除生成不同的产物。对氢脱卤/C-O 耦合的进一步动力学研究表明，芳基卤化物的反应阶数为 0.1/0.5，（CN）电子的反应阶数为 1.5/0.03，从而揭示了两种转化的决定速率步骤分别是 NiI 的氧化加成和（CN）电子的转移。我们的工作推动了通过载流子在光活性支持物上的积累来调节芳基卤化物的转化，并指导了金属萘催化平台的设计/操作，以实现目标转化。

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来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.