Synergistic electronic structure modulation in single-atomic Ni sites dispersed on Ni nanoparticles encapsulated in N-rich carbon nanotubes synthesized at low temperature for efficient CO2 electrolysis

IF 20.2 1区 化学 Q1 CHEMISTRY, PHYSICAL
Ramireddy Boppella , Youngsam Kim , K. Arun Joshi Reddy , Inae Song , Yaeeun Eom , Eunji Sim , Tae Kyu Kim
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Abstract

Ni, N-doped carbon materials (Ni–N–C) are prosperous candidates for the electrochemical CO2 reduction reaction (CO2RR) due to their outstanding activity and selectivity. However, the role of the coexisting uncoordinated N-doped sites and Ni nanoparticles (Ni-NPs) in overall CO2RR has been overlooked in prior studies. To address this gap, a low temperature synthesis method developed for Ni-NP-encapsulated Ni–N–C nanotube (Ni-NCNT) catalysts with atomically dispersed Ni–N4 and abundant uncoordinated N-doped sites, where Ni-NPs increase the electron density on Ni–N–C nanotube through carbon network and synergistically enhances the CO2RR activity. The systematic analysis reveals the cooperative role of Ni-NPs and uncoordinated N-doped sites in altering the electronic structure of Ni–N4 sites. The results of control experimental studies confirm the synergistic interaction of uncoordinated N-doped sites boost the CO2RR activity of Ni–N4 sites. Additionally, density functional theory calculations show that the strong interaction between the Ni-NPs and Ni–N–C did not affect the electronic structures of the Ni–N4 centers, but rather alter the electronic structure of uncoordinated pyridinic-N sites. This variation led to decreased the energy barriers of rate-limiting steps of COOH* formation on Ni–N4 and N-doped sites, resulting in excellent CO2RR performance.

Abstract Image

分散在低温合成的富含 N 的碳纳米管中的镍纳米粒子上的单原子镍位点的协同电子结构调制,用于高效 CO2 电解
掺杂镍、氮的碳材料(Ni-N-C)因其出色的活性和选择性而成为电化学二氧化碳还原反应(CO2RR)的理想候选材料。然而,之前的研究忽略了共存的非配位掺杂 N 位点和镍纳米颗粒(Ni-NPs)在整个 CO2RR 中的作用。针对这一空白,研究人员开发了一种低温合成 Ni-NP 封装 Ni-N-C 纳米管(Ni-NCNT)催化剂的方法,该催化剂具有原子分散的 Ni-N4 和丰富的非配位 N 掺杂位点,Ni-NPs 通过碳网络增加了 Ni-N-C 纳米管上的电子密度,协同提高了 CO2RR 活性。系统分析揭示了 Ni-NPs 和非配位 N 掺杂位点在改变 Ni-N4 位点电子结构中的协同作用。对照实验研究结果证实了非配位掺杂 N 位点的协同作用提高了 Ni-N4 位点的 CO2RR 活性。此外,密度泛函理论计算表明,Ni-NPs 和 Ni-N-C 之间的强相互作用并没有影响 Ni-N4 中心的电子结构,而是改变了未配位吡啶-N 位点的电子结构。这种变化降低了 Ni-N4 和掺杂 N 的位点上 COOH* 形成的限速步骤的能障,从而使 CO2RR 具有优异的性能。
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来源期刊
Applied Catalysis B: Environmental
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.
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