Chinese Journal of Catalysis最新文献_第7页

Na2CO3-assisted synthesis of Na-doped crystalline/amorphous g-C3N4 S-scheme homojunction photocatalyst for enhanced H2O2 production na2co3辅助合成na掺杂结晶/非晶g-C3N4 S-scheme均结光催化剂促进H2O2生成

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64849-2

Lihong Tan , Xinhe Wu , Jiachao Xu , Mahmoud Sayed , Guohong Wang

The construction of crystalline/amorphous g-C₃N₄ homojunctions presents a versatile strategy to obtain all-organic homojunction photocatalysts with better interface matching and lower interface charge carrier movement resistance for optimized photocatalytic activity. However, the process entails a complex multi-step workup, which compromises its feasibility. To overcome this challenge, this work provided an innovative Na₂CO₃-induced crystallinity modulation strategy to construct a Na-doped crystalline/amorphous g-C₃N₄ S-scheme homojunction photocatalyst in a single step. The approach involves the initial pre-assembling of melamine and cyanuric acid molecules, and subsequent introduction of Na₂CO₃ before the calcination. Na₂CO₃ plays key roles to induce in-situ crystallinity modulation during the calcination and as a source for Na-doping. The prepared g-C₃N₄ S-scheme homojunction photocatalyst demonstrated a prominent H₂O₂-production rate of 444.6 μmol·L^–1·h^–1, which is 6.1-fold higher than that of bulk g-C₃N₄. The enhanced activity was attributed to the synergistic effect of charge carrier separation induced by the S-scheme homojunction system, and the optimized interfacial H₂O₂ generation kinetics. The latter was fostered by the Na-doping. This study provides an innovative approach for the one-step construction of g-C₃N₄ S-scheme homojunction and its integration in photocatalytic applications.

构建晶态/非晶态g-C3N4同质结是获得具有较好界面匹配和较低界面载流子移动阻力的全有机同质结光催化剂的一种通用策略，可优化光催化活性。然而，这个过程需要一个复杂的多步骤的工作，这损害了其可行性。为了克服这一挑战，本工作提供了一种创新的na2co3诱导结晶度调制策略，以一步构建na掺杂晶体/非晶g- c3n4s -scheme同质结光催化剂。该方法包括最初的三聚氰胺和三聚氰尿酸分子的预组装，随后在煅烧前引入Na2CO3。在煅烧过程中，Na2CO3在诱导原位结晶度调制中起着关键作用，并作为na掺杂的来源。制备的g-C3N4 s -方案均结光催化剂的h2o2产率为444.6 μmol·L-1·h-1，是本体g-C3N4的6.1倍。活性的增强主要是由于s -图式均结体系诱导的载流子分离的协同作用，以及优化的界面H2O2生成动力学。后者是由钠兴奋剂促成的。本研究为一步构建g-C3N4 s -图式均结及其在光催化应用中的集成提供了一种创新方法。

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引用次数: 0

Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO2 reduction 结合控制合成和理论揭示单原子镍催化剂在电化学CO2还原中的活性位点结构

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64759-0

Yuxing Xu , Leilei Wang , Qin Liu , Botao Teng , Chuanqiang Wu , Binghui Ge , Wentuan Bi , Minghui Gu , Mengkai Zhang , Huan Yan , Junling Lu

Electrocatalytic conversion of carbon dioxide (CO₂) offers an effective method of CO₂ fixation to mitigate global warming and the energy crisis. However, for supported Ni single-atom catalysts (SACs), which are among the most promising candidates for this application, the relationship between Ni coordination structure and catalytic properties is still under strong debate. Here, we fabricated a series of Ni SACs through precise-engineering of anchor sites on nitrogen-doped carbon (NC) followed by Ni atom anchoring using atomic layer deposition. Among them, a Ni₁/NC SAC, with a coordination number (CN) of four but less pyridinic nitrogen (N_pyri), achieved over 90% faradaic efficiency for CO at potentials from –0.7 to –1.0 V and a mass activity of 6.5 A/mg_Ni at –0.78 V along with high stability, outperforming other Ni SACs with lower CN and more N_pyri. Theoretical calculations of various three and four-coordinated Ni₁-N_xC_y structures revealed a linear correlation between the reaction Gibbs free energy for the potential–limiting step and the highest occupied molecular orbital (HOMO) position of Ni-3d orbitals, therein the four-coordinated Ni₁-N₁C₃ with the highest HOMO position is identified as the active site for the electrocatalytic CO₂-to-CO process, in line with the experimental results.

二氧化碳的电催化转化为减缓全球变暖和能源危机提供了一种有效的二氧化碳固定方法。然而，对于负载型镍单原子催化剂（SACs）来说，镍配位结构与催化性能之间的关系仍然存在激烈的争论。在这里，我们通过在氮掺杂碳（NC）上精确设计锚点，然后使用原子层沉积技术将Ni原子锚定，从而制备了一系列Ni SACs。其中，配位数（CN）为4而吡啶氮（Npyri）较少的Ni1/NC SAC在-0.7 ~ -1.0 V电势下对CO的法拉第效率超过90%，在-0.78 V电势下的质量活度为6.5 a /mgNi，稳定性好，优于其他CN较低、Npyri较高的Ni SAC。对各种三配位和四配位Ni1-NxCy结构的理论计算表明，限制电位步骤反应的吉布斯自由能与Ni-3d轨道的最高占据分子轨道（HOMO）位置呈线性相关，其中HOMO位置最高的四配位Ni1-N1C3被确定为电催化CO2-to-CO过程的活性位点，与实验结果一致。

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引用次数: 0

Lattice oxygen transfer induced active phase transition of VPO catalysts in cross condensation of acetic acid and formaldehyde 晶格氧转移诱导VPO催化剂在乙酸与甲醛交叉缩合反应中的活性相变

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64844-3

Yinhong Niu , Zhen Shi , Zhiquan Yu , Qiang Guo , Junju Mu , Yafei Liang , Zhixin Zhang , Sheng Wang , Feng Wang

Vanadium phosphorus oxide (VPO) catalyst is a promising candidate for the condensation reaction of formaldehyde (FA) and acetic acid (HAc) to produce acrylic acid (AA). However, the complexity of the active phases and their dynamic interconversion under redox conditions has led to controversies regarding the actual active phase in this reaction. To address this, this study systematically investigates the phase transition and underlying mechanism of VPO catalysts under reaction conditions. X-ray diffraction (XRD) patterns, Raman spectra, transmission electron microscopy images and X-ray photoelectron spectroscopy collectively demonstrated that the V⁴⁺ phase (VO)₂P₂O₇ retained the bulk phase structure throughout the reaction, with only minor surface phase transition observed. In contrast, the V⁵⁺ phase underwent reduction to other phases in both bulk and surface regions. Specifically, the δ-VOPO₄ phase rapidly transformed into the α_II-VOPO₄ phase, which could reversibly convert into the R1-VOHPO₄ phase (V⁴⁺). Controlled variable experiments, H₂-temperature programmed reduction and in-situ XRD experiments in a hydrogen atmosphere further demonstrated that these phase transitions were primarily attributed to the loss of lattice oxygen. The presence of V⁴⁺ phase in VPO catalysts enhanced the selectivity of acrylic acid, while the existence of V⁵⁺ phase promoted the activation of acetic acid. This work elucidates the redox-driven phase evolution of VPO catalysts and offers valuable insights for designing efficient catalysts for FA-HAc cross-condensation by balancing phase stability and activity.

钒磷氧化物（VPO）催化剂是甲醛（FA）与乙酸（HAc）缩合制丙烯酸（AA）的一种很有前途的催化剂。然而，活性相的复杂性及其在氧化还原条件下的动态相互转化导致了该反应中实际活性相的争议。为了解决这一问题，本研究系统地研究了VPO催化剂在反应条件下的相变及其潜在机理。x射线衍射（XRD）图、拉曼光谱、透射电镜图像和x射线光电子能谱共同表明，V4+相（VO）2P2O7在整个反应过程中保持了体相结构，仅观察到少量的表面相变。相比之下，V5+相在体区和表面区域都还原为其他相。其中δ-VOPO4相快速转化为αII-VOPO4相，αII-VOPO4相可可逆转化为R1-VOHPO4相（V4+）。可控变量实验、h2 -温度程序还原实验和氢气氛下的原位XRD实验进一步证明了这些相变主要是由于晶格氧的损失。VPO催化剂中V4+相的存在增强了丙烯酸的选择性，而V5+相的存在促进了乙酸的活化。这项工作阐明了氧化还原驱动的VPO催化剂的相演化，并为通过平衡相稳定性和活性来设计FA-HAc交叉缩合的高效催化剂提供了有价值的见解。

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引用次数: 0

Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries 静电纺丝技术与MOFs的结合：架起高性能锌空气电池发展的桥梁

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64817-0

Haotian Guo , Lulu Zhao , Xinyu Liu , Jing Li , Pengfei Wang , Zonglin Liu , Linlin Wang , Jie Shu , Tingfeng Yi

Metal-organic frameworks (MOFs) are porous materials formed by the coordination of organic and inorganic components through coordination bonds. MOF-derived materials preserve the large surface area and inherent porosity of their parent structures, while simultaneously offering enhanced electrical conductivity and more efficient charge transport. Studies have shown that integrating electrospinning with MOFs into continuous nanofiber networks can effectively address issues such as MOF structural collapse, low conductivity, and leaching of active sites. Moreover, the electrospinning technique enables fine-tuning of the product’s morphology, architecture, and chemical composition, thereby unlocking new possibilities for advancing high-performance ZABs. This review provides a systematic overview of recent advances in non-precious metal electrocatalysts derived from electrospun-MOF composites and examines the unique advantages of combining electrospinning with MOF precursors in the design of oxygen electrocatalysts. It also investigates the morphological regulation of various fiber structures, including porous, hollow, core-shell, and beaded structures, as well as their influence on the catalytic performance. Finally, the performance enhancement strategies of electrospun-MOF catalyst materials are examined, and the development prospects along with future research directions related to oxygen electrocatalysts based on electrospun nanofibers are emphasized. This thorough review aims to offer meaningful insights and practical guidance for advancing the understanding, design, and fabrication of next-generation devices for energy conversion and storage.

金属有机骨架（mof）是由有机和无机组分通过配位键配合而形成的多孔材料。mof衍生材料保留了其母体结构的大表面积和固有孔隙率，同时提供了增强的导电性和更有效的电荷传输。研究表明，将静电纺丝与MOF结合成连续的纳米纤维网络可以有效地解决MOF结构崩溃、电导率低、活性位点浸出等问题。此外，静电纺丝技术可以对产品的形态、结构和化学成分进行微调，从而为推进高性能ZABs提供了新的可能性。本文系统综述了电纺丝-MOF复合材料制备非贵金属电催化剂的最新进展，并探讨了电纺丝与MOF前驱体相结合在氧电催化剂设计中的独特优势。研究了不同纤维结构的形态调控，包括多孔、空心、核壳和珠状结构，以及它们对催化性能的影响。最后，对电纺丝- mof催化剂材料的性能增强策略进行了探讨，并对电纺丝纳米纤维氧电催化剂的发展前景和未来的研究方向进行了展望。这篇全面的综述旨在为推进下一代能量转换和存储设备的理解、设计和制造提供有意义的见解和实用指导。

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引用次数: 0

Synergistic catalysis of oxygen vacancy and S-scheme heterojunction in NiFe2O4–x/NiS regulates peroxymonosulfate activation forenhanced photo-Fenton-like reaction NiFe2O4-x /NiS中氧空位和s型异质结的协同催化调控过氧单硫酸盐活化增强光- fenton -like反应

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64841-8

Yan Wang , Xiaorui Yan , Zeyang Sun , Jinjun Liu , Yiwen Wang , Chenchao Hu , Yilin Deng , Meng Xie , Jimin Xie , Wei Zhang , Yuanguo Xu

The regulation of peroxymonosulfate (PMS) activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle. This work demonstrates a strategy to constructed ethylene glycol (EG) well-coupled S-scheme heterojunction of NiFe₂O_4–x/NiS with oxygen vacancy (V_O)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation, a 99% PMS decomposition efficiency is achieved. Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe₂O_4–x/NiS with an S-scheme heterojunction, which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation. The S-scheme NiFe₂O_4–x/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate (0.15 min^–1) at a low PMS dosage of 0.1 g/L, which is 19 times greater than that of the pristine NiS (0.0077 min^–1). Density functional theory calculations confirmed that V_O in NiFe₂O_4–x/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer. Moreover, in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation, unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe₂O_4–x/NiS during the reaction. This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation, providing a promising solution the cost-effective and efficient treatment of organic wastewater.

通过构建氧空位和非均相界面催化来调节过氧单硫酸盐（PMS）的活化对难降解污染物的氧化至关重要，但仍然是一个主要的障碍。本研究展示了一种构建乙二醇（EG）良好耦合的氧空位（VO）修饰的NiFe2O4-x /NiS的S-scheme异质结的策略，通过光激发激活PMS来有效地去除污染物，PMS的分解效率达到99%。光辅助开尔文探针力显微镜和原位电子自旋共振验证了在具有s型异质结的NiFe2O4-x /NiS中建立了一致的电荷转移途径，为有机污染物氧化提供了丰富的活性位点和独特的电荷传输途径。当PMS用量为0.1 g/L时，S-scheme NiFe2O4-x /NiS异质结的降解率显著提高（0.15 min-1），是原始NiS （0.0077 min-1）的19倍。密度泛函理论计算证实，NiFe2O4-x /NiS中的VO有效促进了PMS的吸附，降低了电子转移的能垒。此外，原位实验和实验证据提供了通过光激发激活PMS的机理见解，揭示了反应过程中NiFe2O4-x /NiS上的还原和氧化过程的双途径激活机制。本研究强调了空位工程协同s -方案异质结在开发有效的调节PMS活化催化剂方面的潜力，为经济高效地处理有机废水提供了一个有希望的解决方案。

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引用次数: 0

An eco-friendly photocatalytic coupling capacitive deionization system for efficient chlorophenol wastewater treatment 一种高效处理氯酚废水的生态友好型光催化偶联电容去离子系统

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64839-X

Ziye Zheng , Yi Ren , Meng Dai , Hongsheng Li , Huizhen Cui , Sen Wang , Shuguang Wang , Zuoli He

Since conventional photocatalytic technology fails to achieve complete elimination of chlorophenol contaminants from aqueous environments, this study presents a synergistic photocatalysis-capacitive deionization (PC-CDI) system as an advanced solution for industrial chlorophenol wastewater remediation. The PC-CDI system, employing boron nitride/carbon nitride (BN/CN) heterojunction electrodes, demonstrates exceptional degradation performance toward chlorophenols. The high-surface-area porous BN/CN heterojunction facilitates electro-adsorption and charge carrier separation, thereby synergistically optimizing both photocatalytic (PC) and capacitive deionization (CDI) functionalities. Remarkably, the integrated system achieves a 2,4-DCP degradation efficiency of 97.15% and a 2,4,6-TCP degradation efficiency of 100% in 2 h. The CDI component enables spatial separation through the electro-adsorption of Cl^– ions at the anode, effectively mitigating their interference and suppressing chlorinated byproduct formation. Concurrently, the electro-adsorption of positively charged chlorophenol pollutants accelerates their diffusion to catalytic sites, promoting the reactive oxygen species (ROS)-driven degradation of chlorophenol pollutants. The PC-CDI system exhibits robust stability (> 95% efficiency retention over five cycles) and broad applicability across various chlorophenol derivatives. By circumventing Cl^–-induced side reactions and inhibiting chlorine radical generation during photocatalysis, this strategy minimizes the environmental risks associated with chlorinated byproducts during chlorophenol wastewater treatment. These findings establish the PC-CDI system as a sustainable and eco-friendly technology for industrial wastewater treatment.

由于传统的光催化技术无法完全消除水中环境中的氯酚污染物，本研究提出了一种协同光催化-电容去离子（PC-CDI）系统，作为工业氯酚废水修复的先进解决方案。采用氮化硼/氮化碳（BN/CN）异质结电极的PC-CDI系统对氯酚具有优异的降解性能。高表面积多孔BN/CN异质结促进电吸附和电荷载流子分离，从而协同优化光催化（PC）和电容去离子（CDI）功能。值得注意的是，集成系统在2 h内实现了97.15%的2,4- dcp降解效率和100%的2,4,6- tcp降解效率。CDI组件通过在阳极电吸附Cl -离子实现空间分离，有效地减轻了它们的干扰，抑制了氯化副产物的形成。同时，带正电的氯酚污染物的电吸附加速了其向催化位点的扩散，促进了活性氧（ROS）对氯酚污染物的降解。PC-CDI体系表现出强大的稳定性（在5个循环中保持95%的效率）和对各种氯酚衍生物的广泛适用性。通过规避Cl诱导的副反应和抑制光催化过程中氯自由基的产生，该策略将氯酚废水处理过程中与氯化副产物相关的环境风险降至最低。这些发现表明PC-CDI系统是一种可持续的、环保的工业废水处理技术。

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引用次数: 0

Water interactions in molecular sieve catalysis: Framework evolution and reaction modulation 分子筛催化中的水相互作用：框架演化和反应调节

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64828-5

Linhai He , Caiyi Lou , Lu Sun , Jing Niu , Shutao Xu , Yingxu Wei , Zhongmin Liu

Porous molecular sieve catalysts, including aluminosilicate zeolites and silicoaluminophosphate (SAPO) molecular sieves, have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development. Given the ubiquitous presence of water during catalyst synthesis, storage, and application, the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention. These effects are inherently complex and highly dependent on various factors such as temperature, water phase, and partial pressure. In this review, we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis, based on both experimental and theoretical calculation results. Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level, underscoring the dynamic and labile nature of these frameworks in water environments. The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives: (1) its participation in reaction through hydrogen bonding interactions, such as competitive adsorption at active sites, stabilization of ground and transition states, and proton transfer bridge; (2) its role as a direct reactant forming new species via reactions with other guest molecules. Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.

多孔分子筛催化剂，包括铝硅酸盐沸石和硅铝磷酸酯（SAPO）分子筛，在多相催化中得到了广泛的应用，有望在推进碳中和和可持续发展中发挥关键作用。由于水在催化剂的合成、储存和应用过程中无处不在，水与分子筛之间的相互作用及其对框架和催化反应的影响引起了人们的广泛关注。这些影响本质上是复杂的，高度依赖于各种因素，如温度、水相和分压。在这篇综述中，我们基于实验和理论计算结果，全面概述了目前对水分子筛相互作用及其在催化中的作用的理解。特别关注水在原子水平上引起的铝硅酸盐和SAPO框架的可逆和不可逆结构变化，强调了这些框架在水环境中的动态和不稳定性。从两个方面讨论了水对分子筛催化反应的催化性能和反应动力学的影响：(1)水通过氢键相互作用参与反应，如活性位点的竞争性吸附、基态和过渡态的稳定以及质子转移桥；(2)它作为直接反应物通过与其他客体分子反应形成新物质的作用。这一领域的最新进展为水反应催化剂的合理设计和优化提供了有价值的见解。

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引用次数: 0

Hierarchical manganese-containing TS-1 zeolite for the direct oxidation of cyclohexane to adipic acid with molecular oxygen: Synergy between matrix Ti and Mn species 分子氧直接氧化环己烷制己二酸的分级含锰TS-1沸石：基体Ti和Mn的协同作用

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64822-4

Mingdong Zhang, Xueshuang Wu, Guiying Li, Changwei Hu

The direct oxidation of cyclohexane to adipic acid (AA) without the use of HNO₃ is important but still challenging. Herein, hierarchical manganese-containing TS-1 zeolite (HMTS) was prepared using an improved direct synthesis method, in which titanium and manganese coexist within the zeolite matrix, as characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet, extended X-ray absorption fine structure etc. The introduction of matrix Mn species (Mn³⁺, Mn⁴⁺) not only increased the surface oxygen vacancies, but also generated medium-strong acid sites, which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination. On HMTS-3, one-pot oxidation of cyclohexane at 140 °C and 2 MPa O₂ gave 81.6% conversion and 71.5% AA selectivity, the highest value obtained at present. Control experiments with single-component samples confirmed that matrix Ti⁴⁺ catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol (KA oil), and matrix Mn favored the conversion of KA oil to AA. The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity. Specifically, the matrix Ti⁴⁺ might activate oxygen to form Ti-O₂^2– which facilitated the activation of the C–H bond of cyclohexane. The activation of O₂ on matrix Mn³⁺ formed Mn⁴⁺-O₂^– favoring the breaking of the C–C bond of cyclohexanone. The hierarchical structure not only exposed more active sites and promoted mass transfer, but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti, which facilitated the overall reaction. This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.

不使用HNO3直接氧化环己烷生成己二酸（AA）是重要的，但仍然具有挑战性。本文采用改进的直接合成方法制备了钛和锰在分子筛基体内共存的分级含锰分子筛TS-1 (HMTS)，通过x射线衍射、x射线光电子能谱、透射电镜、紫外、扩展x射线吸收等精细结构对其进行了表征。基体Mn （Mn3+, Mn4+）的引入不仅增加了表面氧空位，还生成了中强酸位，使HMTS催化剂具有高效活性氧和促进底物配位的能力。在htms -3上，环己烷在140℃和2 MPa O2条件下一锅氧化，转化率为81.6%，AA选择性为71.5%，是目前最高的。单组分样品对照实验证实，基体Ti4+催化环己烷转化为环己酮和环己醇的混合物（KA油），而基体Mn有利于KA油转化为AA。层状结构中基体Ti和Mn之间的协同作用是形成优异活性的关键因素。具体来说，基体Ti4+可能激活氧形成Ti-O22 -，促进环己烷C-H键的激活。O2在Mn3+基体上的活化形成了有利于环己酮C-C键断裂的Mn4+-O2 -。分层结构不仅暴露了更多的活性位点，促进了传质，而且为基体Mn与基体Ti的协同作用提供了更好的微环境，有利于整体反应的进行。这项工作证明了HMTS的实际应用潜力，并为环己烷直接氧化制AA提供了有益的见解。

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引用次数: 0

Interface-engineered S-scheme 2D/1D heterojunction of Cs0.32WO3/WO3·2H2O for boosted CO2 photoreduction: Synergistic charge separation and activation Cs0.32WO3/WO3·2H2O的S-scheme 2D/1D异质结促进CO2光还原：协同电荷分离和活化

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-11-17 DOI: 10.1016/S1872-2067(25)64818-2

Guangmei Gan , Lin Yin , Xiaotian Wang, Juyuan Xing, Yuan Li, Gaoke Zhang

Developing efficient photocatalysts for CO₂ conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion. In this study, a novel S-scheme heterojunction composed of reduction Cs_0.32WO₃ (CWO) nanosheets with hexagonal structure and oxidation WO₃·2H₂O (WO) nanorods with monoclinic structure photocatalyst was successfully constructed via an ultrasound strategy. Under full-spectrum irradiation for 4 h, the optimized 2D/1D of heterostructure CWO/WO-0.8 exhibited superior photocatalytic performance, achieving CO and CH₃OH yields of 29.74 and 63.71 μmol·g^–1, respectively. The enhanced activity is primarily ascribed to the formation of an S-scheme charge transfer pathway, which facilitates efficient separation and directional migration of photogenerated charge carriers through the internal electric field at the CWO/WO interface. This process facilitates the electron enrichment on the CWO surface and significantly enhances its CO₂ reduction ability. Besides, the results of various characterizations show that CWO/WO-0.8 possesses enhanced optical response capability. The results of density functional theory calculations and CO₂-temperature programmed desorption analysis confirmed that the CWO/WO heterojunction exhibits stronger CO₂ adsorption and activation abilities compared to the pristine CWO and WO. The reaction pathway for CH₃OH production was elucidated by in-situ diffused reflectance Fourier transformed infrared tests. This work provides new insights into the rational design of S-scheme photocatalysts for efficient and selective CO₂ conversion.

在全光谱照射下开发高效的CO2转化光催化剂仍然是太阳能-化学能转换的关键挑战。在本研究中，通过超声策略成功构建了由六方结构的还原型Cs0.32WO3 （CWO）纳米片和单斜结构光催化剂氧化型WO3·2H2O （WO）纳米棒组成的新型S-scheme异质结。在全光谱照射4 h后，优化后的异质结构CWO/WO-0.8的2D/1D光催化性能优异，CO和CH3OH的产率分别为29.74和63.71 μmol·g-1。活性的增强主要是由于形成了S-scheme电荷转移途径，该途径通过CWO/WO界面处的内部电场促进了光生电荷载流子的有效分离和定向迁移。该工艺有利于CWO表面的电子富集，显著提高了其CO2还原能力。此外，各种表征结果表明，CWO/WO-0.8具有增强的光响应能力。密度泛函理论计算和CO2-温度程序解吸分析结果证实，与原始CWO和WO相比，CWO/WO异质结具有更强的CO2吸附和活化能力。通过原位扩散反射傅里叶变换红外测试，阐明了CH3OH生成的反应途径。这项工作为合理设计s型光催化剂以实现高效和选择性的CO2转化提供了新的见解。

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引用次数: 0

Enantioselective induction by G-quadruplex DNA/hemin in intramolecular cyclopropanation 分子内环丙化过程中g -四联体DNA/血红蛋白的对映选择性诱导

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64797-8

Wenhui Miao , Jingya Hao , Wenqin Zhou , Guoqing Jia , Can Li

G-quadruplex DNA (G4) can function as a kind of nucleic acid apoenzyme for constructing G4/hemin biocatalyst to mimic the catalytic function of hemoprotein. However, achieving stereoselective control with G4/hemin remains a persistent challenge. Here, we report that a PW17/hemin (PW17: 5’-GGGTAGGGCGGGTTGGG-3’), adopting the 5’-5’ stacked dimeric parallel G4 topology, can realize the enantioselective induction in intramolecular cyclopropanation of allyl diazoacetates with enantioselectivity up to 87% ee. Spectroscopic characterization and catalytic results demonstrate that the relatively open G-quartet of the 3’ terminal in dimeric PW17 contributes a catalytic pocket for hemin accommodation and plays a pivotal role in enantioselective control. This finding expands the unique repertoire of heme enzyme using biological scaffolds from proteins to nucleic acids and resolves the long-standing challenge of stereochemical control in G4/hemin catalysis.

g -四重体DNA （G4）可作为核酸脱酶，用于构建G4/血红蛋白生物催化剂，模拟血红蛋白的催化作用。然而，实现G4/hemin的立体选择性控制仍然是一个持续的挑战。本文报道了一种PW17/hemin （PW17: 5′-GGGTAGGGCGGGTTGGG-3′），采用5′-5′堆叠二聚体平行G4拓扑结构，可实现重氮乙酸丙烯基环丙化的分子内对映选择性诱导，对映选择性高达87% ee。光谱表征和催化结果表明，二聚体PW17的3′端相对开放的g -四重奏为血红蛋白的调节提供了一个催化口袋，并在对映选择性控制中起关键作用。这一发现扩大了血红素酶使用生物支架从蛋白质到核酸的独特库，并解决了G4/血红素催化中立体化学控制的长期挑战。

引用次数: 0