Journal of Energy Chemistry最新文献_第6页

Solid-phase ion exchange constructs cobalt-promoted Pd/FAU catalysts for simultaneously stable and selective dimethyl carbonate synthesis 固相离子交换构建了钴促进的Pd/FAU催化剂，用于同时稳定和选择性合成碳酸二甲酯

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.jechem.2025.11.037

Chunzheng Wang , Lei Liu , Han Liu , Shicheng Yuan , Miao Li , Weihao Zhang , Girolamo Giordano , Hailing Guo , Svetlana Mintova

The practical application of Pd/FAU catalysts for the gas-phase indirect oxidative carbonylation of methanol to dimethyl carbonate (DMC) is limited by two major challenges: the formation of Brønsted acid sites during catalyst preparation, which reduces DMC selectivity, and the reduction of Pd²⁺ active sites with subsequent formation of large Pd nanoparticles under reaction conditions, leading to catalyst deactivation. To address these issues, we developed a simple and versatile solid-phase grinding method to incorporate a cobalt promoter, yielding Pd-Co/FAU catalysts. Comprehensive characterization using in situ infrared spectroscopy, thermogravimetric analysis-mass spectrometry (TG-MS), and X-ray photoelectron spectroscopy (XPS) confirmed that this approach effectively eliminates Brønsted acid sites through solid-phase ion exchange between Co²⁺ and bridged Si–(OH)–Al groups (CoCl₂ + 2Si–(OH)–Al → Co(Si–(O)–Al)₂ + 2HCl↑), and stabilizes electron-deficient Pd^(2+δ)+ (0 < δ ≤ 2) species via electron transfer from Pd to Co. Compared to the parent Pd/FAU catalyst, the modified Pd-Co/FAU catalyst exhibits significantly improved performance, maintaining 97 % CO conversion and 81 % DMC selectivity for over 100 h with a turnover frequency of 0.26 s⁻¹. This enhanced stability originates from the inhibition of Pd sintering, evidenced by a reduction in Pd particle size from 11.2 nm in Pd/FAU to highly dispersed species in Pd-Co/FAU, and the preservation of active Pd^(2+δ)+ sites. The improved selectivity results from the suppressed decomposition of the CH₃ONO reactant due to the elimination of Brønsted acidity. Furthermore, in situ infrared spectroscopy indicated that DMC formation proceeds via coupling of COOCH₃* (*, active sites) and OCH₃* intermediates on these stabilized electron-deficient Pd sites.

Pd/FAU催化剂在甲醇气相间接氧化羰基化制碳酸二甲酯（DMC）过程中的实际应用受到两个主要挑战的限制：催化剂制备过程中Brønsted酸位的形成降低了DMC的选择性，以及在反应条件下形成大Pd纳米颗粒导致Pd2+活性位点的还原，导致催化剂失活。为了解决这些问题，我们开发了一种简单而通用的固相研磨方法，加入钴促进剂，生产Pd-Co/FAU催化剂。利用原位红外光谱、热重分析-质谱（TG-MS）和x射线光电子能谱（XPS）的综合表征证实，该方法通过Co2+和桥接Si - (OH) - al基团(CoCl2 + 2Si - （OH) - al→Co(Si - (O) - al)2 + 2HCl↑）之间的固相离子交换有效地消除了Brønsted酸位。并通过电子从Pd转移到Co，稳定了缺乏电子的Pd(2+δ)+ (0 < δ≤2)。与母体Pd/FAU催化剂相比，改性Pd-Co/FAU催化剂的性能得到了显著改善，在100 h以上的时间内保持了97%的Co转化率和81%的DMC选择性，周转频率为0.26 s−1。这种增强的稳定性源于对Pd烧结的抑制，Pd/FAU中的Pd粒径从11.2 nm减小到Pd- co /FAU中的高度分散，并且保留了活性Pd(2+δ)+位点。选择性的提高是由于Brønsted酸性的消除抑制了CH3ONO反应物的分解。此外，原位红外光谱表明，DMC的形成是通过COOCH3*（*，活性位点）和OCH3*中间体在这些稳定的缺电子Pd位点上的偶联进行的。

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引用次数: 0

Engineered Co-O-Mo active centers for enhanced water oxidation via lattice oxygen mechanism 设计Co-O-Mo活性中心，通过点阵氧机制增强水氧化

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.jechem.2025.11.036

Fanjun Kong , Heng Zhang , Chengjie Wang , Guikai Zhang , Jing Zhang , Xiaorui Gao , Tao Zhang , Shengqi Chu , Li Song , Shi Tao

Heterostructured transition-metal compounds show great potential in the oxygen evolution reaction (OER), but the reaction mechanism induced by the surface reconstruction remains unclear. Herein, we develop a kind of Co-O-Mo active center in Co oxyhydroxide (MoCoOOH) via in situ reconstruction, which exhibits an overpotential of 275 mV at 10 mA cm⁻² in alkaline conditions, as well as negligible deactivation after durability operation driven by a solar cell. The operando tests reveal that Mo accelerates the reconstruction from Co-Se-Mo to Co-O-Mo in MoCoOOH, which triggers the lattice oxygen activation for enhanced intrinsic OER activity. Theoretical calculations demonstrate that the Mo atoms can optimize the d-orbital energy level of Co metal atoms, adsorption-desorption oxygenated intermediates, and the rate-determining step barrier. This work gives deep insights into the oxygen-involved mechanism in the reconstructed phase and inspires the rational design of high-activity electrocatalysts in multi-electron reactions.

异质结构过渡金属化合物在析氧反应（OER）中表现出很大的潜力，但其表面重构引发的反应机制尚不清楚。在此，我们通过原位重构的方法在氢氧Co （MoCoOOH）中开发了一种Co- o- mo活性中心，该活性中心在碱性条件下在10 mA cm - 2下表现出275 mV的过电位，并且在太阳能电池驱动下持久运行后失活可以忽略不计。operando实验表明，Mo加速了MoCoOOH中Co-Se-Mo到Co-O-Mo的重构，触发了晶格氧活化，增强了OER活性。理论计算表明，Mo原子可以优化Co金属原子的d轨道能级、吸附-解吸氧化中间体和决定速率的阶位垒。本研究对重构相的含氧机理有了深入的认识，对多电子反应中高活性电催化剂的合理设计具有启发意义。

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引用次数: 0

Phase content regulation of P2/O3-type biphasic layered oxides for stable sodium ion storage P2/ o3型两相层状氧化物相含量调控对钠离子的稳定储存

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.jechem.2025.11.035

Liang Gao , Xue-Yan Wu , Xuheng Jiang , Jing-Zhe Wan , Jia-Ning Yang , Shang-Qi Li , Qinfeng Zheng , Yixiao Zhang , Jie-Sheng Chen , Kai-Xue Wang

P2/O3 composite layered transition metal oxides (LTMOs), constructed by elemental doping, markedly improve sodium storage performance. However, the influence of the doped elements, which usually contribute to electrochemical activity, on the electrochemical performance of the resulting biphasic materials could hardly be ruled out. Herein, three compositionally identical P2/O3-Na_0.67Fe_0.42Li_0.08Mn_0.45Sn_0.05O₂ materials are synthesized by calcination at 900 °C for 14, 12, and 10 h, yielding P2/O3 ratios of approximately 6:1, 3:1, and 2:3, respectively. The resulting materials are designated as PO61, PO31, and PO23, respectively. Cycled at 1 C within the voltage range of 2.0–4.5 V, an initial discharge capacity of 118.3 mAh g⁻¹ is delivered by PO31, with a retention rate of 81.1% after 100 cycles, significantly outperforming those of PO61 (106.8 mAh g⁻¹, 65.0%) and PO23 (83.9 mAh g⁻¹, 61.5%). Systematic investigation of the charge/discharge behaviour reveals that the mitigated phase transition and enhanced cycling performance in these P2/O3 biphasic materials originate from the formation of shorter Fe–O bonds, which promote structural stabilization. This work provides fundamental insights into phase content regulation and advances the development of LTMOs.

通过元素掺杂构建的P2/O3复合层状过渡金属氧化物（LTMOs）显著提高了钠的存储性能。然而，通常有助于电化学活性的掺杂元素对所得到的双相材料的电化学性能的影响很难被排除。本文在900℃下煅烧14、12和10 h，合成了三种成分相同的P2/O3- na0.67 fe0.42 li0.08 mn0.45 sn0.05 o2材料，得到的P2/O3比分别约为6:1、3:1和2:3。所得材料分别命名为PO61、PO31和PO23。在2.0 ~ 4.5 V电压范围内，在1c条件下循环，PO31的初始放电容量为118.3 mAh g−1，循环100次后的保留率为81.1%，明显优于PO61 （106.8 mAh g−1,65.0%）和PO23 （83.9 mAh g−1,61.5%）。对充放电行为的系统研究表明，这些P2/O3双相材料的相变减缓和循环性能增强源于较短的Fe-O键的形成，这促进了结构的稳定性。这项工作为相含量调节提供了基本的见解，并推动了LTMOs的发展。

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引用次数: 0

Dynamic phase reconstruction enables synergistic ion adsorption and diffusion for high-rate sodium storage 动态相重构可实现离子的协同吸附和扩散，实现高速率的钠存储

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.jechem.2025.11.039

Xiaojun Zhao , Wenqing Zhou , Youlin Yang , Zhen Yang , Zhenyu Dong , Panqing Bai , Anjun Hu , Wei Wang

Tin dioxide (SnO₂) holds promise as an anode material for high-capacity sodium-ion storage. However, its practical use is hindered by low conductivity, sluggish Na⁺ kinetics, and drastic volume changes, leading to inadequate rate capability and cycling stability. Herein, we report the SnO₂/Zn₂SnO₄ nanoparticles uniformly anchored on N-doped graphene nanosheets (SnO₂/ZTO@NGr) anode for sodium-ion batteries/hybrid capacitors (SIBs/SIHCs). A dynamic phase reconstruction during cycling where sodiation-generated Na₁₅Sn₄ and NaZn₁₃ alloys reversibly convert into amorphous SnO₂ and crystalline ZTO upon desodiation, enabling isotropic Na⁺ diffusion through amorphous SnO₂ while leveraging ZTO’s low-energy diffusion pathways (0.37 eV barrier). Density functional theory confirms strong Na⁺ adsorption on SnO₂, synergizing with fast ion mobility on ZTO to boost storage kinetics. The conductive NGr network can prevent nanoparticle aggregation and ensure rapid electron transport, thus contributing to excellent electrochemical performance. The SnO₂/ZTO@NGr anode yields exceptional cycling stability (279 mA h g⁻¹ after 700 cycles at 2 A g⁻¹) and high-rate capability (363 mA h g⁻¹ at 5 A g⁻¹) in SIBs. The assembled SnO₂/ZTO@NGr//AC (activated carbon) SIHCs deliver a high energy density of 122 Wh kg⁻¹ at 200 W kg⁻¹, establishing a new phase-complementary design paradigm coupled with conductive hybridization for advanced energy storage.

二氧化锡（SnO2）有望成为高容量钠离子存储的阳极材料。然而，它的实际应用受到电导率低、Na+动力学缓慢和体积变化剧烈的阻碍，导致速率能力和循环稳定性不足。在此，我们报道了SnO2/Zn2SnO4纳米颗粒均匀锚定在n掺杂石墨烯纳米片（SnO2/ZTO@NGr）阳极上，用于钠离子电池/混合电容器（SIBs/ sihc）。在循环过程中，钠化生成的Na15Sn4和NaZn13合金可逆地转化为非晶态SnO2和结晶ZTO，利用ZTO的低能扩散途径（0.37 eV势垒），使Na+在非晶态SnO2中各向同性扩散。密度泛函理论证实了SnO2对Na+的强吸附，与ZTO上的快速离子迁移协同作用，提高了存储动力学。导电的NGr网络可以防止纳米颗粒聚集，保证电子的快速传递，从而具有优异的电化学性能。SnO2/ZTO@NGr阳极在sib中具有优异的循环稳定性（在2 A g−1下循环700次后279 mA h g−1）和高倍率性能（在5 A g−1下363 mA h g−1）。组装的SnO2/ZTO@NGr//AC（活性炭）sihc在200 W kg - 1时可提供122 Wh kg - 1的高能量密度，为先进的储能技术建立了新的相位互补设计范式，并结合导电杂交。

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引用次数: 0

Beyond the primary solvation sheath: correlating Li+ solvation sheath structure with the electrochemical performances of phosphorus anode 原生溶剂化鞘外：Li+溶剂化鞘结构与磷阳极电化学性能的关系

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-28 DOI: 10.1016/j.jechem.2025.11.034

Xinpeng Han , Siyu Fang , Junhan Pan , Shijie Song , Yuhao Chen , Jie Sun

Instead of designing a primary solvation sheath, the regulation of the secondary solvation sheath is overlooked but critical for manipulating ion migration and interfacial electrochemistry. Herein, we integrate molecular dynamics simulations with experimental measurements to systematically investigate the correlation between the Li⁺ secondary solvation sheath and the electrochemical performance of phosphorus (P) anodes. We find that the bis(fluorosulfonyl)imide anion (FSI⁻)-rich secondary solvation sheath serves as an “electrostatic gear” to pull Li⁺ out of the primary solvation sheath, thereby generating channels through which the Li⁺ can pass. Meanwhile, the compact size of secondary solvation sheath promotes the formation of dense FSI⁻-derived clusters, which in turn enables the construction of a mechanically robust interphase. This unique FSI⁻-rich, compact secondary solvation sheath dictates the performance of the P anode, achieving a durable cycle life of 19 months at 200 mA g⁻¹. After 600 cycles at 2.6 A g⁻¹, the capacity remained at 1540.7 mA h g⁻¹, corresponding to 76.7 % of the 10th discharge capacity with the low decay rate of 0.039 % per cycle. When coupled with the NCM₅₂₃ cathode, the NCM₅₂₃//P full cell configuration maintains 98.4 % capacity retention after 1000 cycles at 0.5C. These findings provide a new insight into handling the electrolyte compatibility and fast-charging issues of P-based lithium-ion batteries.

而不是设计一个初级溶剂化鞘，二级溶剂化鞘的调节被忽视，但对操纵离子迁移和界面电化学至关重要。本文将分子动力学模拟与实验测量相结合，系统地研究了Li+二次溶剂化鞘层与磷(P)阳极电化学性能之间的关系。我们发现富氟磺酰亚胺阴离子（FSI−）的二次溶剂化鞘层充当“静电齿轮”，将Li+从一次溶剂化鞘层中拉出，从而产生Li+可以通过的通道。与此同时，紧凑的二级溶剂化鞘层促进了密集的FSI衍生团簇的形成，这反过来又使得构建一个机械坚固的界面相成为可能。这种独特的富含FSI−，紧凑的二次溶剂化护套决定了P阳极的性能，在200 mA g−1下实现了19个月的持久循环寿命。在2.6 A g−1下循环600次后，容量保持在1540.7 mA h g−1，相当于第10次放电容量的76.7%，每循环衰减率为0.039%。当与NCM523阴极耦合时，NCM523//P全电池配置在0.5C下循环1000次后保持98.4%的容量保持率。这些发现为处理p基锂离子电池的电解质兼容性和快速充电问题提供了新的见解。

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引用次数: 0

Enhancement of CO2 reduction to C2+ products via local microenvironment modulation on Al2O3/Cu in neutral media 中性介质中Al2O3/Cu局部微环境调制促进CO2还原为C2+产物

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-27 DOI: 10.1016/j.jechem.2025.11.033

Yaqing Hu , Mingxia Zhou , Kunyu Xu , Zihao Yang , Zhaoxia Dong

The electroreduction of carbon dioxide to multi-carbon products (C₂₊) represents an effective pathway for achieving carbon cycling and high-density renewable energy storage. However, its practical implementation is challenged by excessively high C–C coupling reaction energy barriers and competitive hydrogen evolution reaction (HER). Modifications to the local microenvironment play a decisive role in the three-phase interface reaction of CO₂ electrocatalytic reduction. Therefore, this study employed an Al₂O₃-modified copper catalyst (Al₂O₃/Cu) to modulate the local reaction microenvironment, thereby promoting C₂₊ formation. Notably, the optimized Al₂O₃/Cu catalyst achieved a remarkable C₂₊ Faraday efficiency (FE) of 71.3% at −1.33 V vs. RHE (reversible hydrogen electrode; all potentials herein are referenced to RHE) in a neutral electrolyte using a flow cell, significantly outperforming unmodified Cu catalysts. This catalyst also demonstrated excellent catalytic stability, exceeding 56 h. Theoretical calculations and in situ spectroscopic characterization confirmed that introduced Al₂O₃ species kinetically facilitate water dissociation and proton consumption, which is crucial for maintaining a transient localized high-pH environment under operating conditions. This alkaline microenvironment not only suppresses the HER but also stabilizes the critical Cu²⁺/Cu⁺ active sites against over-reduction, while simultaneously lowering the energy barrier of C–C coupling reactions. This work underscores the critical role of dynamically modulating the localized chemical environment in neutral electrolytes for CO₂ reduction reactions (CO₂RR), offering novel insights for designing such microenvironments.

二氧化碳电还原成多碳产物（C2+）是实现碳循环和高密度可再生能源储存的有效途径。然而，其实际实施受到了过高的C-C偶联反应能垒和竞争性析氢反应（HER）的挑战。在CO2电催化还原的三相界面反应中，局部微环境的改变起着决定性的作用。因此，本研究采用Al2O3修饰的铜催化剂（Al2O3/Cu）来调节局部反应微环境，从而促进C2+的生成。值得注意的是，优化后的Al2O3/Cu催化剂在- 1.33 V下与RHE（可逆氢电极，此处所有电位均参考RHE）相比，在使用流动电池的中性电解质中获得了71.3%的C2+法拉第效率（FE），显著优于未改性的Cu催化剂。该催化剂还表现出优异的催化稳定性，超过56小时。理论计算和原位光谱表征证实，引入的Al2O3物质在动力学上促进了水的解离和质子的消耗，这对于在操作条件下维持短暂的局部高ph环境至关重要。这种碱性微环境不仅抑制了HER，而且稳定了临界Cu2+/Cu+活性位点，防止过度还原，同时降低了C-C偶联反应的能垒。这项工作强调了动态调节中性电解质中二氧化碳还原反应（CO2RR）的局部化学环境的关键作用，为设计这种微环境提供了新的见解。

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引用次数: 0

Multifunctional ethyl dimethylphosphonoacetate for passivating defects and modulating crystallization for high performance air-processed perovskite solar cells 多功能二甲基膦乙酸乙酯用于钝化缺陷和调制高性能空气处理钙钛矿太阳能电池的结晶

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-27 DOI: 10.1016/j.jechem.2025.11.029

Congcong Liu , Ning Luo , Lichun Zhang , Zhongqiang Wang

High performance air-processed perovskite solar cells (PSCs) are described as critical enablers for low-cost commercial production. Nonetheless, the grain boundaries/surface defects and uncontrollable crystallization of air-processed perovskite films prevent the enhancement of efficiency and stability of air-processed PSCs. Herein, a multifunctional ethyl dimethylphosphonoacetate (EDPA) with multiple complex sites is embedded into air-processed perovskite films to synergistically passivate the GBs/surface defects and modulate the perovskite crystallization. The multi-site electron-donating groups (PO and CO) in EDPA can firmly coordinate with the uncoordinated Pb²⁺/Pb clusters on the GBs/surface, thereby effectively passivating the defects of air-processed perovskite films. The coordination effect delays the crystallization of the perovskite, enlarging the average grain size of the perovskite from 478 to 677 nm, which can effectively suppress non-radiative recombination and prolong carrier lifetime. Consequently, the air-processed device with EDPA deliver an impressive efficiency of 23.10 %, which is one of the highest efficiencies achieved in an air environment with a relative humidity of 45 %. EDPA-incorporated devices without encapsulation reveal preeminent humidity and thermal stability, retaining 81 % of their original efficiency under constant illumination for 1500 h. The work affords a new strategy for passivating defects of air-processed perovskite layers, which advances the commercial application of efficient and stable devices.

高性能空气处理钙钛矿太阳能电池（PSCs）被描述为低成本商业生产的关键推动者。然而，空气处理钙钛矿薄膜的晶界/表面缺陷和不可控结晶阻碍了空气处理psc效率和稳定性的提高。本文将具有多个复合位点的多功能二甲基膦乙酸乙酯（EDPA）嵌入到空气处理的钙钛矿薄膜中，以协同钝化gb /表面缺陷并调节钙钛矿结晶。EDPA中的多给电子基团（PO和CO）能与GBs/表面未配位的Pb2+/Pb团簇牢固配位，从而有效钝化气处理钙钛矿膜的缺陷。配位效应延缓了钙钛矿的结晶，使钙钛矿的平均晶粒尺寸从478 nm增大到677 nm，可以有效抑制非辐射复合，延长载流子寿命。因此，带有EDPA的空气处理装置提供了23.10%的令人印象深刻的效率，这是在相对湿度为45%的空气环境中实现的最高效率之一。未封装edpa的器件显示出卓越的湿度和热稳定性，在恒定光照1500小时下保持其原始效率的81%。该工作为空气处理钙钛矿层的钝化缺陷提供了一种新的策略，促进了高效和稳定器件的商业应用。

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引用次数: 0

Machine learning accelerates the design and discovery of single-atom catalysts for electrochemical reactions 机器学习加速了电化学反应单原子催化剂的设计和发现

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-26 DOI: 10.1016/j.jechem.2025.11.031

Shiyan Wang , Chaopeng Liu , Weiyao Hao , Xianjun Zhu , Xianghong Niu , Dongwei Ma , Longlu Wang , Qiang Zhao

Single-atom catalysts (SACs) stand at the forefront of catalysis research, attributable to their distinctive electronic structure, maximized atomic utilization, and exceptional catalytic performance, making them highly promising for renewable energy and sustainable energy conversion applications. However, their complex design parameters—including metal active sites, coordination environments, and substrate interactions—pose significant challenges for traditional experimental and computational approaches. These limitations hinder the systematic understanding of structure–property relationships in SACs. Machine learning (ML) offers a powerful alternative, enabling rapid screening and rational design by uncovering hidden patterns in high-dimensional catalyst data. This review summarizes recent advances in applying ML to the design and discovery of SACs. First, we analyze and summarize the recent trends and representative works in ML applications for SACs research. Next, a systematic workflow is proposed to guide researchers through ML-assisted SACs discovery, from data engineering to model application. We then showcase ML’s impact on critical catalytic reactions—CO₂RR, HER, NRR, and ORR/OER—demonstrating its ability to uncover high-performance catalysts. Finally, we discuss challenges and future directions for integrating ML with SAC research, aiming to inspire innovative solutions and interdisciplinary collaboration. By bridging ML and catalysis, this review provides researchers with a practical roadmap to expedite the advancement of SACs.

单原子催化剂（SACs）由于其独特的电子结构、最大限度的原子利用率和优异的催化性能，站在催化研究的前沿，在可再生能源和可持续能源转换应用中具有很大的前景。然而，它们复杂的设计参数——包括金属活性位点、协调环境和底物相互作用——对传统的实验和计算方法提出了重大挑战。这些限制阻碍了对SACs结构-性质关系的系统理解。机器学习（ML）提供了一个强大的替代方案，通过揭示高维催化剂数据中的隐藏模式，实现快速筛选和合理设计。本文综述了将机器学习应用于sac的设计和发现方面的最新进展。首先，我们分析和总结了机器学习应用于sac研究的最新趋势和代表性作品。接下来，提出了一个系统的工作流程来指导研究人员通过ml辅助sac发现，从数据工程到模型应用。然后，我们展示了ML对关键催化反应（co2rr， HER， NRR和ORR/ oer）的影响，展示了其发现高性能催化剂的能力。最后，我们讨论了将ML与SAC研究相结合的挑战和未来方向，旨在激发创新的解决方案和跨学科的合作。通过桥接ML和催化，这篇综述为研究人员提供了一个实用的路线图，以加快SACs的进步。

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引用次数: 0

Manipulating chemical environment via entropy configuration to facilitate cationic redox reactions in Na4Fe1.5Mn1.5(PO4)2P2O7 通过熵组态操纵化学环境促进Na4Fe1.5Mn1.5(PO4)2P2O7中的阳离子氧化还原反应

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-26 DOI: 10.1016/j.jechem.2025.11.032

Jiahao Gu, Liang He, Xu Wang, Xiaochen Ge, Wen Zhou, Yanqing Lai, Zhian Zhang

The redox reaction of Fe/Mn ions in Na₄Fe_1.5Mn_1.5(PO₄)₂(P₂O₇) (NMFPP) is expected to achieve the unity of high energy density and long lifespan. Nonetheless, the efficiency and reversibility of the reaction hardly reach expectations, arising from the poor conductivity and structure stability. Herein, an entropy configuration strategy is proposed to address these issues. Introducing Ni/Co ions with abundant valence electrons can increase the configurational entropy of the system and trigger the reconstruction of the chemical environment, involving electronic structure, coordination environment, and atomic arrangement. The interaction between Ni/Co and host atoms will alter hybrid orbital energy and electron distribution, thereby narrowing the bandgap and improving conductivity. Besides, inert Ni/Co can stabilize the coordination environment of surrounding Na⁺ during the reaction process to ensure smooth diffusion channels, which facilitates ion transport. Notably, the disruption of short-range order generated by high configurational entropy will block the distortion transmission of the Jahn-Teller effect on structure. Consequently, the cationic redox reaction in Na₄Mn_1.3Fe_1.5Ni_0.1Co_0.1(PO₄)₂P₂O₇ (NMFPP-NC) exhibits outstanding efficiency and reversibility, which endows it with high specific energy and cycle stability. This work reveals the structure-activity relationship between entropy configuration and chemical environment, inspiring the development of high-performance sodium ion batteries.

Fe/Mn离子在Na4Fe1.5Mn1.5(PO4)2(P2O7) （NMFPP）中的氧化还原反应有望实现高能量密度和长寿命的统一。然而，由于电导率和结构稳定性差，反应的效率和可逆性难以达到预期。本文提出了一种熵配置策略来解决这些问题。引入具有丰富价电子的Ni/Co离子可以增加体系的构型熵，引发化学环境的重建，包括电子结构、配位环境和原子排列。Ni/Co与主原子之间的相互作用将改变杂化轨道能量和电子分布，从而缩小带隙，提高电导率。此外，惰性Ni/Co在反应过程中稳定了周围Na+的配位环境，保证了扩散通道的畅通，有利于离子的传递。值得注意的是，高位态熵所产生的短程秩序的破坏将阻止jann - teller效应在结构上的畸变传输。因此，Na4Mn1.3Fe1.5Ni0.1Co0.1(PO4)2P2O7 （NMFPP-NC）中的阳离子氧化还原反应表现出优异的效率和可逆性，从而使其具有高比能和循环稳定性。这项工作揭示了熵态与化学环境之间的构效关系，对高性能钠离子电池的开发具有启发意义。

{"title":"Manipulating chemical environment via entropy configuration to facilitate cationic redox reactions in Na4Fe1.5Mn1.5(PO4)2P2O7","authors":"Jiahao Gu, Liang He, Xu Wang, Xiaochen Ge, Wen Zhou, Yanqing Lai, Zhian Zhang","doi":"10.1016/j.jechem.2025.11.032","DOIUrl":"10.1016/j.jechem.2025.11.032","url":null,"abstract":"<div><div>The redox reaction of Fe/Mn ions in Na4Fe1.5Mn1.5(PO4)2(P2O7) (NMFPP) is expected to achieve the unity of high energy density and long lifespan. Nonetheless, the efficiency and reversibility of the reaction hardly reach expectations, arising from the poor conductivity and structure stability. Herein, an entropy configuration strategy is proposed to address these issues. Introducing Ni/Co ions with abundant valence electrons can increase the configurational entropy of the system and trigger the reconstruction of the chemical environment, involving electronic structure, coordination environment, and atomic arrangement. The interaction between Ni/Co and host atoms will alter hybrid orbital energy and electron distribution, thereby narrowing the bandgap and improving conductivity. Besides, inert Ni/Co can stabilize the coordination environment of surrounding Na+ during the reaction process to ensure smooth diffusion channels, which facilitates ion transport. Notably, the disruption of short-range order generated by high configurational entropy will block the distortion transmission of the Jahn-Teller effect on structure. Consequently, the cationic redox reaction in Na4Mn1.3Fe1.5Ni0.1Co0.1(PO4)2P2O7 (NMFPP-NC) exhibits outstanding efficiency and reversibility, which endows it with high specific energy and cycle stability. This work reveals the structure-activity relationship between entropy configuration and chemical environment, inspiring the development of high-performance sodium ion batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 248-257"},"PeriodicalIF":14.9,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145798312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhanced hole–proton-coupled electron transfer of spin polarized photocatalyst via Mo–S4 coordination for sequential activation of C(sp3)H and OH bonds 通过Mo-S4配位增强自旋极化光催化剂的空穴-质子耦合电子转移，以顺序激活C(sp3)H和OH键

IF 14.9 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2025-11-26 DOI: 10.1016/j.jechem.2025.11.030

Xiaoping Wang , Bowen Yang , Haoye Wang , Haixin Guo , Richard Lee Smith Jr , Yaqiong Su , Xinhua Qi

Photocatalytic oxidative dehydrogenation of biomass feedstocks offers the possibility for synthesizing value-added chemicals, but the sluggish transport kinetics and rapid recombination of photogenerated charge carriers constrain photocatalysis efficiency. Spin-polarized photocatalysts, by accelerating the separation of photogenerated electrons and holes, offer a promising strategy for selective biomass valorization. Herein, polarization unit Mo was incorporated into ZnIn₂S₄ (ZIS) with S-vacancy through Mo–S₄ coordination (Mo-Vs-ZIS) to enhance hole and proton-coupled electron transfer (PCET). Mo-Vs-ZIS spin polarized photocatalyst applied to 5-hydroxymethylfurfural (HMF) afforded a 2,5-diformylfuran (DFF) selectivity of 92.3 % at a production rate of 1105.3 µmol g_cat⁻¹ h⁻¹, attributed to carrier transport and reaction processes. The Mo-Vs-ZIS photocatalyst efficiently (100 min) converted benzyl and furfuryl alcohols, aromatic alcohols bearing electron-rich substituents, and halogen-substituted aromatic alcohols into their corresponding aldehydes. Piezoelectric force microscopy (PFM) and Kelvin probe force microscopy analyses (KPFM) revealed that the full-space polarized electric field was formed to drive directional transfer of photogenerated carriers, facilitating bulk-to-surface charge separation. Moreover, Mo-Vs-ZIS showed high Bader charge transfer to O₂, where Mo atomic sites functioned as an electron reservoir, driving the activation of O₂ to form •O₂⁻, a kinetically favorable step for HMF oxidation and induced transfer of holes to activate C(sp³)H bonds, which is a rate-determining step. Then, the critical step of PCET (•O₂⁻ + H⁺ → •OOH) over Mo-Vs-ZIS gave •OOH for OH activation to complete the reaction sequence. This spin-polarized modification strategy featuring atomic-level catalytic sites enables its application to other semiconductor photocatalysts for biomass conversion.

生物质原料的光催化氧化脱氢为合成增值化学品提供了可能，但光生成的载流子的缓慢传递动力学和快速重组限制了光催化的效率。自旋极化光催化剂通过加速光生电子和空穴的分离，为选择性生物质增值提供了一种很有前途的策略。本文通过Mo- s4配位（Mo- vs -ZIS）将极化单元Mo加入到具有s空位的ZnIn2S4 （ZIS）中，以增强空穴和质子耦合电子转移（PCET）。Mo-Vs-ZIS自旋极化光催化剂对5-羟甲基糠醛（HMF）的选择性为92.3%，产率为1105.3µmol gcat−1 h−1，归因于载流子输运和反应过程。Mo-Vs-ZIS光催化剂能在100 min内有效地将苯基和糠醇、含富电子取代基的芳香醇和卤素取代的芳香醇转化为相应的醛类。压电力显微镜（PFM）和开尔文探针力显微镜（KPFM）分析表明，形成了全空间极化电场来驱动光生载流子的定向转移，促进了体-表面电荷分离。此外，Mo- vs - zis表现出向O2的高Bader电荷转移，其中Mo原子位点作为电子库，驱动O2活化形成•O2−，这是HMF氧化和诱导空穴转移激活C（sp3）氢键的动力学有利步骤，这是一个决定速率的步骤。然后，在Mo-Vs-ZIS上进行PCET（•O2−+ H+→•OOH）的关键步骤，使•OOH活化OH，完成反应序列。这种具有原子级催化位点的自旋极化修饰策略使其能够应用于其他用于生物质转化的半导体光催化剂。

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引用次数: 0