Journal of Energy Chemistry最新文献_第2页

Valence electron matching law for MXene-based single-atom catalysts 基于 MXene 的单原子催化剂的价电子匹配定律

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-19 DOI: 10.1016/j.jechem.2024.10.006

Single-atom catalysts (SACs) have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity. In this study, we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates (O, N, C, and H) in MXene-anchored SACs (M-Ti₂C/M-Ti₂CO₂). The density functional theory results demonstrated that the sum of the valence electron number (V_M) of the interface-doped metal and the valence electron number (V_A) of the adsorbed intermediates in M-Ti₂C followed the 10-valence electron matching law. Furthermore, based on the 10-valence electron matching law, we deduced that the sum of the valence electron number (k) and V_M for the molecular adsorption intermediate interactions in M-Ti₂CO₂ adhered to the 11-valence electron matching law. Electrostatic repulsion between the interface electrons in M-Ti₂CO₂ and H₂O weakened the adsorption of intermediates. Furthermore, we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction, specifically for N₂ → NNH conversion, in the M-Ti₂CO₂ structure. The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate (R² up to 0.970) for catalyst design. Our study introduced a valence electron matching principle between doped metals (single atoms) and adsorbed intermediates (atomic and molecular) for MXene-based catalysts, providing new insights into the design of high-performance SACs.

单原子催化剂（SAC）因其可调节的催化活性而在能源和环境科学领域引起了广泛关注。在本研究中，我们研究了 MXene-anchored SACs（M-Ti2C/M-Ti2CO2）中单原子与吸附中间产物（O、N、C 和 H）之间价电子数的匹配。密度泛函理论结果表明，M-Ti2C 中界面掺杂金属的价电子数（VM）与吸附中间产物的价电子数（VA）之和遵循 10 价电子匹配定律。此外，根据 10 价电子匹配定律，我们推断出 M-Ti2CO2 中分子吸附中间体相互作用的价电子数（k）和 VM 之和遵循 11 价电子匹配定律。M-Ti2CO2 和 H2O 中界面电子之间的静电排斥削弱了中间产物的吸附。此外，我们还应用 11 价电子匹配定律来指导氮还原反应催化剂的设计，特别是 M-Ti2CO2 结构中 N2 → NNH 转化催化剂的设计。我们使用确定的独立性筛选和稀疏化算子算法拟合了一个简单的吸附剂三维描述符（R2 高达 0.970），用于催化剂设计。我们的研究为基于 MXene 的催化剂引入了掺杂金属（单原子）和吸附中间体（原子和分子）之间的价电子匹配原理，为高性能 SAC 的设计提供了新的见解。

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引用次数: 0

Design principles of novel Zn fluorocarboxylate protection layer toward durable dendrite-free Zn metal anodes 新型氟羧酸锌保护层的设计原理--实现耐用的无枝晶锌金属阳极

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-18 DOI: 10.1016/j.jechem.2024.10.004

Aqueous Zn ion batteries (ZIBs) have received extensive attention due to their intrinsic safety, high abundance, and low cost. However, uncontrolled dendrite growth and water-induced side reactions at electrode/electrolyte interfaces hinder the advancement of ZIBs. Herein, density functional theory (DFT) calculation indicates that Zn heptafluorobutyrate can facilitate uniform Zn²⁺ deposition by leveraging the abundant zincophilic groups (e.g., –COO⁻ and –CF) and inhibit water-induced side reactions due to the presence of hydrophobic carbon chains. A Zn heptafluorobutyrate protective layer (denoted as ZFA) is constructed on the metallic Zn surface in situ by acid etching process to control Zn²⁺ desolvation and nucleation behaviors, ensuring enhanced reversibility and stability of Zn anodes. Consequently, the Zn@ZFA anode demonstrates stable operation for more than 2200 h at 1 mA cm⁻² and over 7300 cycles at 40 mA cm⁻², with high Coulombic efficiency of 99.8% over 1900 cycles at 5 mA cm⁻². Impressively, Zn@ZFA||VO₂ full cell achieves exceptional cycle life (204 mA h g⁻¹ after 750 cycles at 3 A g⁻¹) and remarkable rate performance (236 mA g⁻¹ at 10 A g⁻¹). This work provides an insightful guidance for constructing a protection layer of dendrite-free Zn anodes for high-performance ZIBs.

锌离子水电池（ZIBs）因其固有的安全性、高丰度和低成本而受到广泛关注。然而，在电极/电解质界面上不受控制的枝晶生长和水引发的副反应阻碍了 ZIB 的发展。在此，密度泛函理论（DFT）计算表明，七氟丁酸锌可利用丰富的亲锌基团（如 -COO- 和 -CF）促进 Zn2+ 的均匀沉积，并因疏水碳链的存在而抑制水引起的副反应。通过酸蚀刻工艺在金属锌表面原位构建了七氟丁酸锌保护层（简称 ZFA），以控制 Zn2+ 的脱溶和成核行为，从而确保提高锌阳极的可逆性和稳定性。因此，Zn@ZFA 阳极在 1 mA cm-2 下可稳定运行 2200 小时以上，在 40 mA cm-2 下可稳定运行 7300 个周期以上，在 5 mA cm-2 下可稳定运行 1900 个周期以上，库仑效率高达 99.8%。令人印象深刻的是，Zn@ZFA||VO2 全电池实现了超长的循环寿命（在 3 A g-1 条件下循环 750 次后达到 204 mA h g-1）和卓越的速率性能（在 10 A g-1 条件下达到 236 mA g-1）。这项工作为构建高性能 ZIB 的无枝晶 Zn 阳极保护层提供了深刻的指导。

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引用次数: 0

Upcycling of monomers derived from waste polyester plastics via electrocatalysis 通过电催化技术实现废聚酯塑料单体的升级再循环

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-18 DOI: 10.1016/j.jechem.2024.10.005

Electrocatalysis offers efficient and targeted conversion of monomers derived from waste polyester plastics to chemical products under ambient temperature and pressure conditions. This review provides analysis of research on electrochemical upgrading of monomers derived from waste polyester plastics published from 2021 to present. Factors for assessing upgrading of waste polyester plastics include alkaline hydrolysis pretreatment, indices of electrochemical reaction process (activity, stability, and techno-economic analysis), separation, and product recovery. Types of depolymerization monomers and their value-added products are summarized along with electrocatalytic mechanisms and reaction pathways. Notably, cathode coupled reactions offer significant value for anodic waste plastic oxidation during electrolysis processes. Development of bifunctional electrocatalysts can reduce the cost of coupled systems and complexity of the electrolyzer. Upgrading and recycling of waste plastic monomers using electrocatalytic technology should undergo downstream processing to form high-value products containing C–N and C–S derived functional groups obtained from depolymerized monomers. Electrochemical conversion and upgrading of monomers derived from waste polyester plastics can contribute to industrialization and global economies and help to realize environmental sustainability.

在常温常压条件下，电催化技术可将从废聚酯塑料中提取的单体高效、有针对性地转化为化学产品。本综述分析了 2021 年至今发表的有关废聚酯塑料单体电化学升级的研究。评估废聚酯塑料升级的因素包括碱性水解预处理、电化学反应过程指标（活性、稳定性和技术经济分析）、分离和产品回收。此外，还总结了解聚单体的类型及其增值产品，以及电催化机理和反应途径。值得注意的是，阴极耦合反应为电解过程中的阳极废塑料氧化提供了重要价值。开发双功能电催化剂可以降低耦合系统的成本和电解槽的复杂性。利用电催化技术升级和回收废塑料单体时，应进行下游处理，以形成从解聚单体中获得的含有 C-N 和 C-S 衍生官能团的高价值产品。利用电化学技术转化和升级从废弃聚酯塑料中提取的单体，可为工业化和全球经济做出贡献，并有助于实现环境的可持续发展。

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引用次数: 0

Integrating Cu+/Cu0 sites on porous nitrogen-doped carbon nanofibers for stable and efficient CO2 electroreduction to multicarbon products 在多孔掺氮碳纳米纤维上整合 Cu+/Cu0 位点，稳定高效地将二氧化碳电还原为多碳产品

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-17 DOI: 10.1016/j.jechem.2024.09.059

The Cu⁺/Cu⁰ sites of copper-based catalysts are crucial for enhancing the production of multicarbon (C₂₊) products from electrochemical CO₂ reduction reaction (eCO₂RR). However, the unstable Cu⁺ and insufficient Cu⁺/Cu⁰ active sites lead to their limited selectivity and stability for C₂₊ production. Herein, we embedded copper oxide (CuO_x) particles into porous nitrogen-doped carbon nanofibers (CuO_x@PCNF) by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu₂O particles. The porous nitrogen-doped carbon nanofibers protected and dispersed Cu⁺ species, and its microporous structure enhanced the interaction between CuO_x and reactants during eCO₂RR. The obtained CuO_x@PCNF created more effective and stable Cu⁺/Cu⁰ active sites. It showed a high Faradaic efficiency of 62.5% for C₂₊ products in H-cell, which was 2 times higher than that of bare CuO_x (∼31.1%). Furthermore, it achieved a maximum Faradaic efficiency of 80.7% for C₂₊ products in flow cell. In situ characterization and density functional theory (DFT) calculation confirmed that the N-doped carbon layer protected Cu⁺ from electrochemical reduction and lowered the energy barrier for the dimerization of *CO. Stable and exposed Cu⁺/Cu⁰ active sites enhanced the enrichment of *CO and promoted the C–C coupling reaction on the catalyst surface, which facilitated the formation of C₂₊ products.

铜基催化剂的 Cu+/Cu0 位点对于提高电化学二氧化碳还原反应（eCO2RR）中多碳（C2+）产物的产量至关重要。然而，不稳定的 Cu+ 和不足的 Cu+/Cu0 活性位点导致它们在生产 C2+ 时的选择性和稳定性有限。在此，我们通过热解含有 ZIF-8 和 Cu2O 颗粒的电纺纤维膜，将氧化铜（CuOx）颗粒嵌入多孔掺氮碳纳米纤维（CuOx@PCNF）中。多孔掺氮碳纳米纤维保护并分散了 Cu+ 物种，其微孔结构增强了 eCO2RR 过程中 CuOx 与反应物之间的相互作用。获得的 CuOx@PCNF 创造了更有效、更稳定的 Cu+/Cu0 活性位点。在 H-cell 中，C2+ 产物的法拉第效率高达 62.5%，是裸 CuOx（31.1%）的 2 倍。此外，在流动池中，C2+ 产物的法拉第效率最高可达 80.7%。原位表征和密度泛函理论（DFT）计算证实，掺杂 N 的碳层保护了 Cu+ 免受电化学还原，并降低了 *CO 的二聚化能垒。稳定和暴露的 Cu+/Cu0 活性位点增强了 *CO 的富集，促进了催化剂表面的 C-C 偶联反应，从而促进了 C2+ 产物的形成。

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引用次数: 0

Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural 铂修饰金属钴缺陷位点以实现 5-羟甲基糠醛的高效电催化氧化

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-17 DOI: 10.1016/j.jechem.2024.09.054

Co₃O₄ possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural (HMF). However, the enrichment and activation effects of Co₃O₄ on OH⁻ and HMF are weak, which limits its further application. Metal defect engineering can regulate the electronic structure, optimize the adsorption of intermediates, and improve the catalytic activity by breaking the symmetry of the material, which is rarely involved in the upgrading of biomass. In this work, we prepare Co₃O₄ with metal defects and load the precious metal platinum at the defect sites (Pt-Vco). The results of in-situ characterizations, electrochemical measurements, and theoretical calculations indicate that the reduction of Co–Co coordination number and the formation of Pt–Co bond induce the decrease of electron filling in the antibonding orbitals of Co element. The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH⁻ species, thus exhibiting excellent HMF oxidation activity (including a lower onset potential (1.14 V) and 19 times higher current density than pure Co₃O₄ at 1.35 V). In summary, this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail, provides a new option for improving the HMF oxidation activity of cobalt-based materials, broadens the application field of metal defect based materials, and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.

Co3O4 具有直接和间接氧化作用，被认为是一种很有前景的 5-hydroxymethylfurfural (HMF) 氧化催化剂。然而，Co3O4 对 OH- 和 HMF 的富集和活化效应较弱，限制了其进一步应用。金属缺陷工程可以调节电子结构，优化中间产物的吸附，并通过打破材料的对称性来提高催化活性，而这在生物质升级中很少涉及。在这项工作中，我们制备了具有金属缺陷的 Co3O4，并在缺陷位点上负载贵金属铂（Pt-Vco）。原位表征、电化学测量和理论计算的结果表明，Co-Co 配位数的减少和 Pt-Co 键的形成导致 Co 元素反键轨道中电子填充的减少。由此产生的 Co 的 d 带中心上移与 Pt 物种的吸附特性协同增强了有机分子和 OH- 物种的富集和活化，从而表现出优异的 HMF 氧化活性（包括较低的起始电位（1.14 V）和比纯 Co3O4 高 19 倍的电流密度（1.35 V））。综上所述，该研究详细探讨了贵金属修饰金属缺陷位点的吸附增强机理，为提高钴基材料的 HMF 氧化活性提供了新的选择，拓宽了金属缺陷基材料的应用领域，为金属缺陷位点在生物质转化中的功能化利用提供了创新性指导。

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引用次数: 0

Constructing electrochemically stable single crystal Ni-rich cathode material via modification with high valence metal oxides 通过改性高价金属氧化物构建电化学性能稳定的单晶富镍阴极材料

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-17 DOI: 10.1016/j.jechem.2024.09.056

Single crystal Ni-rich cathode materials (SCNCM) are a good supplement in the market of nickel-based materials due to their safety and excellent electrochemical performance. However, the challenges of cation mixing, phase change during charge/discharge, and low thermal stability remain unresolved in single crystal particles. To address these issues, SCNCM are rationally modified by incorporating transition metal (TM) oxides, and the influence of metal ions with different valence states on the electrochemical properties of SCNCM is methodically explored through experimental results and theoretical calculations. Enhanced structural stability is demonstrated in SCNCM after the modifications, and the degree of improvement in the matrix materials varies depending on the valence state of doped TM ions. The highest structural stability is found in WO₃-modified SCNCM, due to the smaller effective ion radii, higher electro-negativity, stronger W–O bond, and efficient suppression of oxygen vacancy generation. As a result, WO₃-modified SCNCM have outstanding cycle performance, with a capacity retention rate of 90.2% after 200 cycles. This study provides an insight into the design of advanced SCNCM with enhanced reversibility and cyclability.

单晶富镍阴极材料（SCNCM）因其安全性和优异的电化学性能而成为镍基材料市场的良好补充。然而，单晶颗粒仍未解决阳离子混合、充放电过程中的相变以及热稳定性低等难题。为了解决这些问题，我们通过加入过渡金属（TM）氧化物对 SCNCM 进行了合理改性，并通过实验结果和理论计算，有条不紊地探讨了不同价态的金属离子对 SCNCM 电化学性能的影响。改性后，SCNCM 的结构稳定性得到增强，基体材料的改善程度因掺杂 TM 离子的价态而异。由于 WO3 改性 SCNCM 的有效离子半径更小、电负性更高、W-O 键更强以及能有效抑制氧空位的产生，因此其结构稳定性最高。因此，WO3 改性 SCNCM 具有出色的循环性能，200 次循环后的容量保持率高达 90.2%。这项研究为设计具有更强可逆性和循环性的先进 SCNCM 提供了启示。

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引用次数: 0

Sulfur doping and oxygen vacancy in In2O3 nanotube co-regulate intermediates of CO2 electroreduction for efficient HCOOH production and rechargeable Zn-CO2 battery In2O3 纳米管中的硫掺杂和氧空位共同调节 CO2 电还原的中间产物，实现高效 HCOOH 生产和可充电 Zn-CO2 电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-16 DOI: 10.1016/j.jechem.2024.09.057

By manipulating the distribution of surface electrons, defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO₂ reduction reaction (CO₂RR). Herein, we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping (V_o-S_x-In₂O₃) for improved CO₂-to-HCOOH electroreduction and Zn-CO₂ battery. The componential synergy significantly reduces the *OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for *HCOOH desorption. As a result, the CO₂RR performance of V_o-S_x-In₂O₃ outperforms Pure-In₂O₃ and V_o-In₂O₃, where V_o-S₅₃-In₂O₃ exhibits a maximal HCOOH Faradaic efficiency of 92.4% at −1.2 V vs. reversible hydrogen electrode (RHE) in H-cell and above 92% over a wide window potential with high current density (119.1 mA cm⁻² at −1.1 V vs. RHE) in flow cell. Furthermore, the rechargeable Zn-CO₂ battery utilizing V_o-S₅₃-In₂O₃ as cathode shows a high power density of 2.29 mW cm⁻² and a long-term stability during charge–discharge cycles. This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO₂RR.

通过操纵表面电子的分布，缺陷工程可以有效控制二氧化碳还原反应（CO2RR）中吸附剂与活性位点之间的吸附能。在此，我们报告了一种含有氧空位和硫掺杂的空心氧化铟纳米管（Vo-Sx-In2O3），用于改进 CO2 到 HCOOH 的电还原和 Zn-CO2 电池。这种成分协同作用大大降低了 *OCHO 的形成障碍，从而加快了质子化过程，并为 *HCOOH 的解吸创造了有利的电子微环境。因此，Vo-Sx-In2O3 的 CO2RR 性能优于 Pure-In2O3 和 Vo-In2O3，其中 Vo-S53-In2O3 在氢电池中与可逆氢电极（RHE）相比，在 -1.2 V 时的 HCOOH 法拉第效率最高可达 92.4%，而在流动电池中，在宽窗口电位下的电流密度较高（与 RHE 相比，在 -1.1 V 时为 119.1 mA cm-2），其 CO2RR 效率高于 92%。此外，利用 Vo-S53-In2O3 作为阴极的可充电 Zn-CO2 电池显示出 2.29 mW cm-2 的高功率密度和充放电循环过程中的长期稳定性。这项工作为阐明共缺陷催化剂在调节高效 CO2RR 的中间产物方面提供了一个有价值的视角。

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引用次数: 0

Stabilizing water and regulating interfacial electrostatic interaction with economical supporting salt for stable Zn metal anode 稳定水和调节与经济型支撑盐的界面静电相互作用，实现稳定的金属锌阳极

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-16 DOI: 10.1016/j.jechem.2024.10.003

Developing rechargeable aqueous Zn batteries for large-scale energy storage is impeded by inadequate reversibility and stability of the Zn anode, primarily caused by parasitic reactions and heterogeneous deposition. This study proposes an economical electrolyte strategy to address these Zn-related issues. The addition of a supporting salt enhances the thermodynamic stability of water, reduces the number of highly reactive water molecules, and modulates the interfacial electrostatic interaction. This approach effectively suppresses hydrogen evolution reaction and uncontrolled deposition. Remarkably, the rationally proportioned electrolyte allows a high average Coulombic efficiency of 99.93% for 1000 cycles in a Zn||Cu battery and a prolonged lifespan exceeding 4800 h in Zn||Zn cells. The knock-on effect is that Zn||MnO₂ pouch cells deliver stable cycling performance, demonstrating the viability of this approach for practical applications.

主要由寄生反应和异质沉积引起的锌阳极可逆性和稳定性不足阻碍了用于大规模储能的可充电锌水电池的开发。本研究提出了一种经济的电解质策略来解决这些与锌相关的问题。添加支撑盐可增强水的热力学稳定性，减少高活性水分子的数量，并调节界面静电相互作用。这种方法能有效抑制氢演化反应和不受控制的沉积。值得注意的是，合理配比的电解质使得锌||铜电池在 1000 次循环中的平均库仑效率高达 99.93%，并延长了锌||锌电池超过 4800 小时的寿命。其连锁效应是，Zn||MnO2 袋装电池具有稳定的循环性能，证明了这种方法在实际应用中的可行性。

引用次数: 0

Dual-phase interface engineering via parallel modulation strategy for highly reversible Zn metal batteries 通过并行调制策略实现双相界面工程，打造高度可逆的金属锌电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-16 DOI: 10.1016/j.jechem.2024.09.053

The reversibility and stability of aqueous Zn metal batteries (AZMBs) are largely limited by Zn dendrites and interfacial parasitic reactions. Herein, we propose a parallel modulation strategy to boost the reversibility of the Zn anode by introducing N,N,N’,N’-tetramethylchloroformamidinium hexafluorophosphate (TCFH) as an additive in the electrolyte. TCFH is composed of PF₆⁻ and TN⁺ with opposite charges. PF₆⁻ can spontaneously induce the in-situ generation of ZnF₂ solid electrolyte interface (SEI) on the anode, which can improve the transport kinetics of Zn²⁺ at the interface, thus promoting the rapid and uniform deposition of Zn as well as inhibiting the growth of dendrites. In addition, TN⁺ is enriched at the anode surface during Zn deposition through the anchoring effect, which brings a reconfiguration of the ion/molecule distribution. The anchored-TN⁺ reduces the concentrations of H₂O and SO₄²⁻, sufficiently restraining the parasitic reaction. Thanks to the dual-phase interface engineering constructed of PF₆⁻ and TN⁺ in parallel, the symmetric cell with the proposed electrolyte survives long cycling stability over 750 h at 20 mA cm⁻², 10 mAh cm⁻². This study offers a distinct viewpoint to the multidimensional optimization of Zn anodes for high-performance AZMBs.

水性锌金属电池（AZMB）的可逆性和稳定性在很大程度上受到锌枝晶和界面寄生反应的限制。在此，我们提出了一种并行调制策略，通过在电解液中引入 N,N,N',N'-四甲基氯甲脒六氟磷酸盐（TCFH）作为添加剂来提高锌阳极的可逆性。TCFH 由带相反电荷的 PF6- 和 TN+ 组成。PF6- 能在阳极上自发地诱导原位生成 ZnF2 固体电解质界面（SEI），从而改善 Zn2+ 在界面上的传输动力学，促进 Zn 的快速均匀沉积，并抑制枝晶的生长。此外，在 Zn 沉积过程中，TN+ 通过锚定效应富集在阳极表面，从而带来离子/分子分布的重新配置。锚定的 TN+ 降低了 H2O 和 SO42- 的浓度，充分抑制了寄生反应。得益于 PF6- 和 TN+并行构建的双相界面工程，使用所提议的电解质的对称电池在 20 mA cm-2 和 10 mAh cm-2 条件下可长期稳定循环 750 小时。这项研究为高性能 AZMB 的锌阳极的多维优化提供了一个独特的视角。

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引用次数: 0

Electro-functionalized 2D nitrogen-carbon nanosheets decorated with symbiotic cobalt single-atoms/clusters 用共生钴单原子/簇装饰的电功能化二维氮碳纳米片

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-16 DOI: 10.1016/j.jechem.2024.09.052

Two-dimensional (2D) materials loaded with single atoms and clusters are being set at the forefront of catalysis due to their distinctive geometric and electronic features. However, the usually-complicated synthesis procedures impede in-depth clarification of their catalytic mechanisms. To this end, herein we developed an efficient one-step dimension-reduction carbonization strategy, with which we successfully architected a highly-efficient catalyst for oxygen reduction reaction (ORR), featured with symbiotic cobalt single atoms and clusters decorated in two-dimensional (2D) ultra-thin (3.5 nm thickness) nitrogen-carbon nanosheets. The synergistic effects of the two components afford excellent oxygen reduction activity in alkaline media (E_1/2 = 0.823 V vs. RHE) and thereof a high power density (146.61 mW cm⁻²) in an assembled Zn-air battery. As revealed by theoretical calculations, the cobalt clusters can regulate electrons surrounding those individual atoms and affect the adsorption of intermediate species. As a consequence, the derived active sites of single cobalt atoms lead to a significant improvement of the ORR performance. Thus, our work may fuel interests to delicate architecture of single atoms and clusters coexisting 2D support toward optimal electrocatalytic performance.

由单个原子和团簇组成的二维（2D）材料因其独特的几何和电子特征而成为催化领域的前沿技术。然而，通常复杂的合成过程阻碍了对其催化机理的深入研究。为此，我们开发了一种高效的一步还原碳化策略，成功地构建了一种高效的氧还原反应（ORR）催化剂，其特点是在二维（2D）超薄（3.5 nm 厚）氮碳纳米片中装饰了共生的钴单原子和团簇。这两种成分的协同效应使其在碱性介质中具有出色的氧还原活性（E1/2 = 0.823 V vs. RHE），并在组装的锌-空气电池中实现了高功率密度（146.61 mW cm-2）。理论计算显示，钴团簇可以调节围绕这些单个原子的电子，并影响中间物质的吸附。因此，单个钴原子衍生出的活性位点显著提高了 ORR 性能。因此，我们的工作可能会激发人们对单个原子和集群共存的二维支持物的微妙结构的兴趣，从而实现最佳的电催化性能。

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引用次数: 0