Journal of Energy Chemistry最新文献_第3页

Thermocatalytic CO2 hydrogenation to high-yield ethanol and C3‒C5 alcohols over promoted Fe-based catalysts 热催化CO2加氢制备高收率乙醇和C3-C5醇

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-14 DOI: 10.1016/j.jechem.2026.01.005

Andrii Kostyniuk, Stanislav Yakushkin, Blaž Likozar

Direct catalytic hydrogenation is an effective approach for CO₂ utilization to produce ethanol and higher alcohols (HA), but developing non-precious metal catalysts with high activity and selectivity remains a major challenge. In this study, we report the development of a highly efficient 4 wt%Rb/25 wt%Cu-25 wt%Zn-50 wt%Fe catalyst, synthesized via the co-precipitation method, for the selective hydrogenation of CO₂ to ethanol and HA in a continuous flow fixed-bed reactor. The catalyst delivers an ethanol space-time yield (STY) of 4.4 mmol g_cat⁻¹ h⁻¹ with 48.8% ethanol selectivity in the gas phase, while the condensed liquid fraction exhibits a maximum C₂₊OH selectivity of 85.3% under 20 bar (H₂/CO₂ = 3) in the temperature range of 200–300 °C over 16–19 h. The superior catalytic performance is attributed to the optimized Rb loading, which enhances structural stability, preserves crystallinity, and mitigates Cu leaching. The Rb-promoting effect on C–C coupling arises from the synergistic interactions among Rb-Cu-Fe, as well as Rb-Cu-Zn. This synergy facilitates the formation of CH₃CH₂O*, CH₃COO*, and CH₃CHO* species on Rb/Cu-Fe₅C₂ and Rb/CuZn sites. Notably, the 4%Rb/CuZnFe catalyst exhibits the most significant modifications in its electronic environment, likely due to changes in oxygen vacancies and altered metal-oxygen interactions upon Rb incorporation. Furthermore, the 4% Rb content plays a critical role in maintaining an optimal balance between catalyst basicity and oxygen vacancies, effectively enhancing CO₂ activation while suppressing side reactions. These findings underscore the potential of Rb-modified CuZnFe catalysts for efficient CO₂ hydrogenation to HA, offering a promising avenue for sustainable chemical production.

直接催化加氢是利用CO2生产乙醇和高级醇（HA）的有效途径，但开发具有高活性和选择性的非贵金属催化剂仍然是一个重大挑战。在本研究中，我们报道了一种高效的4 wt%Rb/25 wt%Cu-25 wt%Zn-50 wt%Fe催化剂的开发，通过共沉淀法合成，用于在连续流固定床反应器中选择性地将CO2加氢成乙醇和HA。该催化剂的乙醇空时产率（STY）为4.4 mmol gcat−1 h−1，气相乙醇选择性为48.8%，而冷凝液组分在20 bar （H2/CO2 = 3）条件下，在200-300℃温度范围内，在16-19 h内，C2+OH选择性最高为85.3%。优化的Rb负载增强了结构稳定性，保持了结晶度，减轻了Cu浸出。Rb-Cu-Fe和Rb-Cu-Zn之间的协同作用促进了C-C耦合。这种协同作用促进了Rb/Cu-Fe5C2和Rb/CuZn位点上CH3CH2O*、CH3COO*和CH3CHO*的形成。值得注意的是，4%Rb/CuZnFe催化剂在其电子环境中表现出最显著的变化，这可能是由于Rb掺入后氧空位的变化和金属-氧相互作用的改变。此外，4%的Rb含量对维持催化剂碱度和氧空位之间的最佳平衡起着关键作用，有效地增强了CO2的活化，同时抑制了副反应。这些发现强调了rb修饰CuZnFe催化剂的潜力，可以有效地将CO2加氢为HA，为可持续化工生产提供了一条有前途的途径。

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引用次数: 0

Stabilizing high-voltage operation of layered oxide cathodes through ionic interdiffusion-triggered surface reinforcement for sodium-ion batteries 通过离子互扩散触发的钠离子电池表面强化来稳定层状氧化物阴极的高压运行

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-14 DOI: 10.1016/j.jechem.2026.01.007

Guohu Chen , Yundian Ya , Yan Li , Guangpeng He , Yuyu Chen , Wenwei Wu , Xuehang Wu

O3-type Ni/Mn-based layered oxides have shown promise for application in sodium ion batteries (SIBs), due to their ability to achieve high energy density at increased upper cut-off voltages through the synergistic cationic/anionic redox reactions. However, a series of interfacial side reactions usually leads to rapid capacity/voltage decay. Herein, we propose a surface reinforcement approach to enable stable 4.5 V high-voltage cycling of O3-type layered oxides. Through thermally induced ionic interdiffusion, Zn(H₂PO₄)₂ acts as a surface reinforcement initiator, enabling the simultaneous achievement of triple effects: elimination of residual alkali, construction of surface coating, and implementation of surface doping. Zn²⁺ doping constructs a special Zn–O–Na/vacancy configuration, enhancing oxygen redox reaction reversibility by increasing non-bonding O 2p states and improving ionic/electronic transport. Additionally, the cubic-structured Na₃₋₂_xZn_xPO₄ (NZP) nanolayer facilitates rapid Na⁺ transfer, restrains lattice oxygen release, and alleviates electrolyte decomposition during cycling. This surface reinforcement treatment diminishes localized asynchronous structural evolution and simplifies the phase transition process during cycling. The surface-reinforced O3-type Na_0.9Cu_0.12Ni_0.33Mn_0.4Ti_0.15O₂ exhibits superior cycling stability (76.8% vs. 48.4% capacity retention over 200 cycles at 100 mA g⁻¹) and rate capability (88.2 vs. 43.1 mAh g⁻¹ at 2000 mA g⁻¹) compared to the pristine counterpart at 4.5 V. This work presents a new approach to fortify the surface structure for developing high-voltage stable layered oxide cathode materials for SIBs.

o3型Ni/ mn基层状氧化物在钠离子电池（sib）中有着广阔的应用前景，因为它们能够在更高的截止电压下通过协同的阳离子/阴离子氧化还原反应获得高能量密度。然而，一系列的界面副反应通常会导致容量/电压的快速衰减。在此，我们提出了一种表面强化方法来实现o3型层状氧化物稳定的4.5 V高压循环。通过热诱导离子相互扩散，Zn(H2PO4)2作为表面增强引发剂，可以同时达到消除残碱、构建表面涂层和实现表面掺杂的三重效果。Zn2+掺杂构建了一种特殊的Zn-O-Na /空位构型，通过增加o2p非键态和改善离子/电子输运来增强氧氧化还原反应的可逆性。此外，立方结构的Na3−2xZnxPO4 （NZP）纳米层促进了Na+的快速转移，抑制了晶格氧的释放，减轻了循环过程中电解质的分解。这种表面强化处理减少了局部的异步结构演变，简化了循环过程中的相变过程。表面增强的o3型Na0.9Cu0.12Ni0.33Mn0.4Ti0.15O2在100 mA g−1下200次循环时的容量保持率为76.8%比48.4%，在2000 mA g−1下的倍率容量为88.2比43.1 mAh g−1。本工作为开发高电压稳定层状氧化阴极材料提供了一种强化表面结构的新方法。

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引用次数: 0

Novel annealing strategy for multi-dimensional optimization in efficient Sb2(S,Se)3 solar cells 高效Sb2(S,Se)3太阳能电池多维优化的新退火策略

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-14 DOI: 10.1016/j.jechem.2026.01.008

Qiqiang Zhu , Yeyang Lin , Mingen Zheng , Weihuang Wang , Lingfeng Zheng , Hongkai Zhu , Yixin Lin , Huiting Du , Qiao Zheng , Hui Deng , Jionghua Wu , Qing Gao , Jianhui Chen , Shuying Cheng

Sb₂(S,Se)₃ solar cells have received extensive attention and development in recent years. However, its performance has been significantly hindered by the unideal quality of Sb₂(S,Se)₃ film restricted by the annealing process. Herein, a low-cost and efficient unidirectional rapid thermal processing (URTP) strategy was first proposed to enhance the quality of Sb₂(S,Se)₃ film. The comprehensive comparative results demonstrated that the URTP strategy could multi-dimensionally optimize the performance of Sb₂(S,Se)₃ films, including the compactness, crystallinity, [hk1] orientation, film conductivity, and density of S vacancy (V_S) defects, by optimizing the film growth mechanism. Consequently, a prominent spike-like conduction band offset (0.36 eV) emerges, accompanied by a widened depletion region and markedly reduced interface carrier recombination in Sb₂(S,Se)₃ solar cells. Interestingly, the URTP strategy inhibited the formation of poorly crystallized clusters at the back interface of Sb₂(S,Se)₃ film, alleviating the localized bandgap mismatch in Sb₂(S,Se)₃ solar cells. Finally, those combined improvements lead to a significant boost in carrier transport, achieving a remarkable efficiency of 10.16% alongside a fill factor (FF) of 68.75%, the best performance during the unconventional annealing strategies. This work not only proposed a novel efficient annealing approach for fabricating high-quality Sb₂(S,Se)₃ film but also brought new insights into the annealing growth mechanism of Sb₂(S,Se)₃ film, thereby boosting the development of Sb₂(S,Se)₃ solar cells.

Sb2(S,Se)3太阳能电池近年来得到了广泛的关注和发展。然而，由于退火工艺的限制，Sb2(S,Se)3薄膜的质量不理想，严重影响了其性能。本文首次提出了一种低成本、高效的单向快速热处理（URTP）策略，以提高Sb2(S,Se)3薄膜的质量。综合比较结果表明，URTP策略可以通过优化薄膜生长机制，从多维度上优化Sb2(S,Se)3薄膜的致密性、结晶度、[hk1]取向、薄膜电导率和S空位（VS）缺陷密度等性能。因此，在Sb2(S,Se)3太阳能电池中，出现了一个突出的尖峰状导带偏移（0.36 eV），伴随着一个扩大的耗尽区和明显减少的界面载流子复合。有趣的是，URTP策略抑制了Sb2(S,Se)3薄膜背面界面上结晶不良的团簇的形成，缓解了Sb2(S,Se)3太阳能电池中局部带隙失配的问题。最后，这些综合改进导致载流子输运的显著提高，实现了10.16%的显著效率和68.75%的填充因子（FF），这是非常规退火策略中的最佳性能。本研究不仅为制备高质量的Sb2(S,Se)3薄膜提供了一种新的高效退火方法，而且对Sb2(S,Se)3薄膜的退火生长机理也有了新的认识，从而促进了Sb2(S,Se)3太阳能电池的发展。

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引用次数: 0

Spatio-temporal ordered transport and site decoupling tandem synergistic catalysis enabling high-load lithium-sulfur batteries 高负荷锂硫电池的时空有序输运和位点解耦串联协同催化

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2025.12.058

Tianmei Xu, Jiafeng Zhu, Tianlong Wu, Yang Zheng, Xinmeng Li, Juan Ding, Jiulin Wang, Yudai Huang

Lithium-sulfur batteries (LSBs) are an attractive option for high-energy-density applications due to their high theoretical capacity and low cost. However, their development is impeded by the shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs). To solve those problems, it is necessary to develop advanced electrocatalysts that can effectively decouple these different pathways while providing complementary active sites. Herein, this work constructs site-specific and spatio-temporal ordered transport Co-MnO heterojunctions via interface engineering, where MnO adsorbs LiPSs and Co promotes the sulfur reduction reaction (SRR). Experimental and theoretical results confirm that MnO adsorption creates a localized high-concentration LiPSs microenvironment for Co sites. The highly active Co then rapidly converts adsorbed LiPSs, suppressing diffusion and preventing site inactivation. This tandem mechanism lowers reaction energy barriers, improves Li₂S nucleation/dissolution kinetics, and enhances LiPSs conversion and overall reaction kinetics. The discharge capacity of LSB with Co-MnO modified-separator reaches 972.6 mAh g⁻¹ at 0.5 C, which remains at 488.0 mAh g⁻¹ after 1000 cycles at 2 C. Even at a high sulfur loading of 6.535 mg cm⁻², the discharge capacity remains at 641.2 mAh g⁻¹ after 200 cycles at 0.2 C. Moreover, Co-MnO simultaneously regulates the uniform lithium deposition and Li⁺ flux to enhance the Li||Li symmetrical cell stably cycled at 2 mA cm⁻² and 2 mAh cm⁻² for 600 h. This study proposes a strategic design for bimetallic tandem reaction electrocatalysts applied to LSBs separators, paving the way for the development of multifunctional separator materials and thereby advancing the performance of next-generation energy storage systems.

锂硫电池（LSBs）由于其高理论容量和低成本而成为高能量密度应用的一个有吸引力的选择。然而，它们的发展受到多硫化锂（LiPSs）的穿梭效应和缓慢的氧化还原动力学的阻碍。为了解决这些问题，有必要开发先进的电催化剂，能够有效地解耦这些不同的途径，同时提供互补的活性位点。本研究通过界面工程构建了特定位点和时空有序输运的Co-MnO异质结，其中MnO吸附LiPSs， Co促进硫还原反应（SRR）。实验和理论结果证实，MnO吸附为Co位点创造了局部高浓度的LiPSs微环境。高活性的Co随后迅速转化吸附的LiPSs，抑制扩散并防止位点失活。这种串联机制降低了反应能垒，改善了Li2S成核/溶解动力学，提高了LiPSs转化和整体反应动力学。Co-MnO改性LSB在0.5℃下的放电容量达到972.6 mAh g−1，在2℃下循环1000次后放电容量仍为488.0 mAh g−1，即使在高硫负荷为6.535 mg cm−2时，在0.2℃下循环200次后放电容量仍为641.2 mAh g−1。Co-MnO同时调节均匀的锂沉积和Li+通量，以增强Li||Li对称电池在2 mA cm - 2和2 mAh cm - 2下稳定循环600 h。本研究提出了应用于LSBs分离器的双金属串联反应电催化剂的战略设计，为多功能分离器材料的开发铺平了道路，从而提高了下一代储能系统的性能。

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引用次数: 0

Suppressing ion migration and electrode corrosion in perovskite solar cells through Nb2O5 interface engineering Nb2O5界面工程抑制钙钛矿太阳能电池中离子迁移和电极腐蚀

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2025.12.060

Shangchen Zhang , Can Li , Xiangyu Liao , Liming Du , Jishan Shi , Xian-Zong Wang , Zhen Li

Ion migration and electrode corrosion limit the operational stability of perovskite solar cells (PSCs), hindering their commercialization. Herein, we demonstrate that Nb₂O₅ films effectively address these challenges when incorporated as buffer layers between the electron transport layer (ETL) and the metal electrode. Electrochemical analysis combined with density functional theory (DFT) calculations reveals that Nb₂O₅ exhibits exceptional corrosion resistance against iodide-induced degradation, effectively blocking bidirectional diffusion of iodide ions and metal atoms. Furthermore, the Nb₂O₅ buffer layer optimizes energy band alignment and interfacial contact, strengthens the built-in electric field, and suppresses non-radiative recombination, enabling efficient electron extraction. As a result of these synergistic effects, the Nb₂O₅ modified PSCs achieve a champion power conversion efficiency (PCE) of 25.85%, with an open-circuit voltage of 1.194 V and a fill factor of 85.35%, significantly outperforming the control device with a PCE of 23.97%. The Nb₂O₅ modified devices demonstrate excellent operational stability. The device retains 94% of its initial PCE after 500 h of maximum power point (MPP) tracking under ambient conditions with 60–65% relative humidity. This cost-effective approach establishes oxide buffer layers as a practical strategy to advance the commercial viability of PSCs, and provides fundamental insights into interface corrosion mechanisms and engineering principles of ETL/electrode interfaces for long-term device stability.

离子迁移和电极腐蚀限制了钙钛矿太阳能电池（PSCs）的运行稳定性，阻碍了其商业化。在此，我们证明Nb2O5薄膜作为电子传输层（ETL）和金属电极之间的缓冲层有效地解决了这些挑战。电化学分析结合密度泛函理论（DFT）计算表明，Nb2O5对碘化物诱导的降解具有优异的耐腐蚀性，有效地阻止了碘离子和金属原子的双向扩散。此外，Nb2O5缓冲层优化了能带对准和界面接触，增强了内置电场，抑制了非辐射复合，实现了高效的电子提取。由于这些协同效应，Nb2O5修饰的PSCs的功率转换效率（PCE）达到了25.85%，开路电压为1.194 V，填充系数为85.35%，显著优于PCE为23.97%的控制器件。Nb2O5改性后的器件表现出良好的运行稳定性。在相对湿度为60-65%的环境条件下，在最大功率点（MPP）跟踪500小时后，该设备仍能保持94%的初始PCE。这种具有成本效益的方法建立了氧化物缓冲层，作为提高psc商业可行性的实用策略，并为ETL/电极界面的长期稳定性提供了界面腐蚀机制和工程原理的基本见解。

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引用次数: 0

Integrative catalytic pairs: four functional pathways toward next-generation multi-intermediate catalysis 整合催化对：新一代多中间体催化的四种功能途径

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2025.12.059

Li Li , Yongfu Sun , Yi Xie

引用次数: 0

Covalent network topology engineering for synergistic ionogels in stable lithium metal batteries 稳定锂金属电池中协同离子凝胶的共价网络拓扑工程

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2026.01.002

Meng Wang, Huangxuanyu Yang, Zhaoyuan Ding, Hu Zhang, Hao Wu, Ruiping Liu

Unraveling the critical role of network topology in ionogel electrolytes, this study demonstrates that a covalent integration strategy is paramount for synergizing mechanical robustness and ion transport. Through a comparative design, a multi-network ionogel featuring covalently anchored poly(ethylene glycol) diacrylate segments within a rigid-flexible liquid crystal polymer/polyacrylamide framework was developed. In contrast to its physically blended counterpart, this covalently engineered ionogel exhibits a well-defined, bi-continuous architecture, as confirmed by multi-scale characterization. This optimized topology confers the material with a remarkable combination of properties: high ionic conductivity (5.55 mS cm^–1), exceptional toughness (3.217 MJ m^–3), and a low activation energy (6.87 kJ mol^–1). Mechanistically, the covalent network not only provides continuous ion pathways but also facilitates the in-situ formation of a stable, LiF/Li₃N-rich solid electrolyte interphase at the electrode-electrolyte interface. Consequently, it enables ultra-stable Li||Li symmetric cells exceeding 1600 h at 0.1 mA cm^–2 and demonstrates excellent performance in Li||LiFePO₄ cells. This work demonstrates that, within the multi-network ionogel design, precise topological control via covalent engineering proves to be a more effective strategy than physical blending for developing high-performance electrolytes for stable lithium metal batteries.

这项研究揭示了网络拓扑在离子凝胶电解质中的关键作用，表明共价整合策略对于协同机械稳健性和离子传输至关重要。通过比较设计，在刚柔液晶聚合物/聚丙烯酰胺框架内开发了一种具有共价锚定聚乙二醇二丙烯酸酯片段的多网络离子凝胶。与物理混合的电离子凝胶相比，这种共价工程的电离子凝胶具有良好定义的双连续结构，多尺度表征证实了这一点。这种优化的拓扑结构赋予了材料显著的性能组合：高离子电导率（5.55 mS cm-1），优异的韧性（3.217 MJ m-3）和低活化能（6.87 kJ mol-1）。从机制上讲，共价网络不仅提供了连续的离子通路，而且还促进了在电极-电解质界面处原位形成稳定的、富含LiF/ li3n的固体电解质界面相。因此，它可以实现在0.1 mA cm-2下超过1600小时的超稳定Li||Li对称电池，并且在Li||LiFePO4电池中表现出优异的性能。这项工作表明，在多网络离子凝胶设计中，通过共价工程进行精确的拓扑控制被证明是一种比物理混合更有效的策略，可以开发用于稳定锂金属电池的高性能电解质。

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引用次数: 0

Unveiling the valid active site of copper nano-electrocatalysts by surface reconstruction for enhanced nitrate reduction to ammonia 通过表面重构揭示铜纳米电催化剂的有效活性位点，促进硝酸还原为氨

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2026.01.001

Jiewen Liu , Susu Duan , Ankang Chen , Xuan Liu , Chuanjin Tian , Nan Gao , Yongming Sui , Bo Zou

Electrochemical conversion of nitrate (NO₃⁻) to ammonia (NH₃) is a prospective way to balance the nitrogen cycle for the environment. Currently, the actual active phase of copper-based materials as nitrate reduction reaction (NO₃⁻RR) catalysts is controversial. Herein, the surface-reconstructed copper nanowires (Cu NWs-SR) with excellent antioxidant properties are proposed to build efficient active sites to promote the NO₃⁻RR, revealing the key role of Cu (111) crystal planes. The electrochemical test results show an average NO₃⁻ conversion of 95% over an ultra-wide NO₃⁻ concentration range (20–500 mM), with NH₃ selectivity of 94% and Faraday efficiency (FE) of 96%, respectively. The catalyst demonstrated high stability of over 100 h, achieving a FE of 93% at a current density of approximately 300 mA cm⁻², with a yield rate of 17.6 mg h⁻¹ cm⁻¹. In situ electrochemical characterization and density functional theory calculations reveal that the reconstructed Cu (111) crystal planes serve as active sites to promote the NO₃⁻RR, while suppressing the hydrogen evolution reaction (HER). This study is valuable in revealing the origin of the active phase of Cu-based catalysts over NO₃⁻RR, which contributes to the catalytic performance across a wide range of NO₃⁻ concentrations.

硝酸盐（NO3−）的电化学转化为氨（NH3）是平衡环境氮循环的一种有前景的途径。目前，铜基材料作为硝酸还原反应（NO3−RR）催化剂的实际活性相存在争议。本文提出了具有优异抗氧化性能的表面重构铜纳米线（Cu NWs-SR），以构建有效的活性位点促进NO3−RR，揭示了Cu（111）晶体平面的关键作用。电化学测试结果表明，在超宽NO3−浓度范围（20 ~ 500 mM）内，NO3−的平均转化率为95%，NH3选择性为94%，法拉第效率（FE）为96%。该催化剂表现出100 h以上的高稳定性，在约300 mA cm−2的电流密度下，FE达到93%，产率为17.6 mg h−1 cm−1。原位电化学表征和密度泛函理论计算表明，重构的Cu（111）晶面是促进NO3−RR的活性位点，同时抑制析氢反应（HER）。这项研究揭示了cu基催化剂在NO3 - RR上的活性相的起源，这有助于在广泛的NO3 -浓度范围内的催化性能。

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引用次数: 0

Synergy of interfacial Co–S bonds and metal bond-connected Cu–Co dual sites for boosting photocatalytic CO2 reduction into ethylene 界面Co-S键和金属键连接的Cu-Co双位点协同作用促进光催化CO2还原成乙烯

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2026.01.003

Qingling Huang , Jie Lin , Jianqiang Hu , Yi Luo , Yicheng Yang , Guobing Zhou , Zhen Yang , Yong Zhou

Photocatalytic CO₂ reduction into valuable C₂₊ products remains a significant challenge, primarily due to inefficient electron transfer and utilization, along with sluggish kinetics in C–C coupling. Herein, we designed and fabricated CoS/CuCo₂S₄ (CS/CCS) hollow-nanosphere heterostructured photocatalysts bridged by interfacial Co–S bonds and containing rich S vacancies (V_S). The interfacial Co–S bonds act as atomic-level channels, facilitating the separation and transfer of photoinduced carriers and concentrating photogenerated electrons mainly on CuCo₂S₄ (CCS) surfaces, significantly enhancing CO₂ photoreduction activity. Moreover, the V_S induces a highly delocalized electron distribution, resulting in increased charge accumulation on the nearby Cu and Co atoms and a consequent shortening of their distance from 3.3 to 2.7 Å. This contributes to the formation of Cu–Co metallic bonds via local metallization. The resulting Cu–Co dual-metal active sites not only transform the endergonic rate-determining step (*CO dimerization to *COCO) on pure CCS into an exergonic one to promote C–C coupling, but also reduce the overall activation energy barrier, synergistically boosting C₂H₄ production. Employing H₂O vapor (which dissociates on the CS surface) as both hydrogen source and hole scavenger, the optimal CS/CCS photocatalyst (CS/CCS-10) achieves a C₂H₄ production rate of 28.79 μmol g⁻¹h⁻¹ with 93.95% electron selectivity (corresponding to 72.14% product selectivity), outperforming most reported photocatalysts under comparable conditions. This work demonstrates a synergistic strategy combining interfacial chemical bonds and metal bond-connected dual-metal sites with the asymmetric charge distribution to fabricate high-performance photocatalysts for CO₂ reduction to C₂₊ products.

光催化CO2还原成有价值的C2+产品仍然是一个重大挑战，主要是由于电子转移和利用效率低下，以及C-C耦合动力学缓慢。本文设计并制备了以Co-S键为界面桥接并含有丰富S空位（VS）的CoS/CuCo2S4 （CS/CCS）空心纳米球异质结构光催化剂。界面Co-S键作为原子级通道，促进了光诱导载流子的分离和转移，并将光生电子主要集中在CuCo2S4 （CCS）表面，显著增强了CO2光还原活性。此外，VS诱导了高度离域的电子分布，导致附近Cu和Co原子上的电荷积累增加，从而使它们的距离从3.3缩短到2.7 Å。这有助于通过局部金属化形成Cu-Co金属键。由此产生的Cu-Co双金属活性位点不仅将纯CCS上的自能速率决定步骤（*CO二聚到*COCO）转变为自能性步骤，促进C-C耦合，而且还降低了总体活化能垒，协同促进C2H4的产生。采用水蒸气（在CS表面解离）作为氢源和空穴清除剂，最佳CS/CCS光催化剂（CS/CCS-10）的C2H4产率为28.79 μmol g−1h−1，电子选择性为93.95%（对应于72.14%的产物选择性），优于目前报道的大多数同等条件下的光催化剂。这项工作展示了一种结合界面化学键和金属键连接的双金属位点与不对称电荷分布的协同策略，以制造高性能光催化剂，用于将CO2还原为C2+产品。

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引用次数: 0

Molecular sieving and skeletal engineering of a pitch precursor to overcome reaction heterogeneity for high-performance hard carbon anodes in sodium-ion batteries 钠离子电池中高性能硬碳阳极沥青前驱体的分子筛分和骨架工程以克服反应非均质性

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jechem.2026.01.004

Zenghao Wang , Bin Lou , Jun Li , Luning Chai , Ning Xiang , Shifu Cheng , Zhichen Zhang , Xiangen Shan , Rongheng Gou , Dong Liu

Pitch-derived hard carbons (HC) are promising anodes for sodium-ion batteries (SIBs) due to their high carbonization yield and low cost. However, the inherent compositional heterogeneity of pitch induces non-uniform oxidative cross-linking during conventional pre-oxidation, which not only renders the microstructure of HC difficult to regulate but also significantly degrades its sodium storage performance. Here, we identify the “shielding effect” of oxidation-inert components in pitch as the root cause of this structural inhomogeneity. To overcome this limitation, we propose a novel “sieving-and-reinforcement strategy”. This involves liquid-phase crosslinking to construct a polar three-dimensional (3D) carbon skeleton, followed by stepwise extraction as a molecular sieving process to remove inert components and expose the reactive skeleton, and finally, oxygen etching as a reinforcement step to drastically enhance the crosslinking density and defect population. This controllably engineered carbon skeleton in-situ evolves into an HC with a uniform hierarchical porous structure, featuring abundant ultra-micropores, optimally sized closed pores (∼2.15 nm), and ultrathin pore walls during carbonization. The resulting HC anode delivers a high reversible capacity of 363.3 mAh g⁻¹ at 50 mA g⁻¹, with an impressive plateau capacity contribution of 71.5%. It also demonstrates exceptional cycling stability, retaining 203.1 mAh g⁻¹ after 500 cycles at a high current density of 1000 mA g⁻¹. This work provides a fundamental understanding of precursor engineering, paving the way for the rational design of advanced carbon materials for next-generation energy storage.

沥青衍生硬碳（HC）具有炭化率高、成本低等优点，是钠离子电池（sib）极具发展前景的阳极材料。然而，沥青固有的组成不均一性导致常规预氧化过程中氧化交联不均匀，不仅使HC的微观结构难以调控，而且显著降低了其储钠性能。在这里，我们确定沥青中氧化惰性成分的“屏蔽效应”是这种结构不均匀的根本原因。为了克服这一限制，我们提出了一种新的“筛分加固策略”。这包括液相交联构建极性三维（3D）碳骨架，随后逐步提取作为分子筛选过程，以去除惰性成分并暴露活性骨架，最后，氧蚀刻作为强化步骤，以大幅提高交联密度和缺陷数量。这种可控工程碳骨架在原位演化成具有均匀分层多孔结构的HC，在碳化过程中具有丰富的超微孔、最佳尺寸的封闭孔（~ 2.15 nm）和超薄孔壁。由此产生的HC阳极在50 mA g - 1时提供363.3 mAh g - 1的高可逆容量，具有令人印象深刻的71.5%的平台容量贡献。它还表现出卓越的循环稳定性，在1000 mA g−1的高电流密度下，500次循环后保持203.1 mAh g−1。这项工作为前体工程提供了基本的理解，为下一代储能先进碳材料的合理设计铺平了道路。

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