Journal of Catalysis最新文献_第3页

Finite-temperature composition–activity maps reveal Cu-rich windows for CO2-to-CO reduction on Ag–Au–Cu–Pd–Pt high-entropy alloys 有限温度组分活度图揭示了Ag-Au-Cu-Pd-Pt高熵合金co -to- co还原的富cu窗口

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-06 DOI: 10.1016/j.jcat.2026.116686

Ni Yi , Qi Xiao , Jilun Song, Shulin Wang, Yingru Wang, Liang Cao

Rational design of multicomponent alloy electrocatalysts is complicated by vast composition space and finite-temperature surface disorder. Here we develop a multiscale framework that links surface thermodynamics to site-resolved energetics for Ag–Au–Cu–Pd–Pt high-entropy alloy (HEA) nanoparticles in CO₂-to-CO reduction. A cluster-expansion Hamiltonian combined with Metropolis Monte Carlo sampling captures temperature-dependent surface segregation and generates realistic equilibrium surface structures. A compact, strain-aware neural network trained on DFT *CO adsorption energies—using ligand, coordination, and strain descriptors—enables high-throughput prediction of adsorption energetics across diverse local environments. Coupled via a Sabatier-type volcano, these predictions yield composition–activity maps that reveal a robust Cu-rich activity window (75–85%). Representative formulations such as Cu_0.85Pt_0.15 and Ag_0.05Au_0.05Cu_0.8Pt_0.05Pd_0.05 exhibit up to ∼5-fold and ∼10-fold higher activity than Cu(111) and equimolar HEAs, respectively, after annealing at 1500 K. DFT-validated analysis identifies a transferable local motif—Cu-atop sites embedded in Cu-enriched first- and second-neighbor shells—that tunes *CO binding toward the volcano optimum and rationalizes the Cu-rich activity ridges. Treating “high entropy” as a design strategy rather than a strict composition rule provides experimentally accessible composition windows and annealing conditions, as well as a reusable workflow for optimizing multicomponent alloy electrocatalysts.

大的成分空间和有限温度的表面无序性使多组分合金电催化剂的合理设计变得复杂。在这里，我们开发了一个多尺度框架，将Ag-Au-Cu-Pd-Pt高熵合金（HEA）纳米颗粒在CO2-to-CO还原过程中的表面热力学与位点分解热力学联系起来。簇展哈密顿量结合大都市蒙特卡罗采样捕获温度依赖的表面偏析，并产生现实的平衡表面结构。一个紧凑的，应变感知的神经网络训练DFT *CO吸附能量-使用配体，配位和应变描述符-使高通量的吸附能量预测在不同的局部环境。结合sabatier类型的火山，这些预测产生的成分活动图揭示了一个强大的富铜活动窗口（75-85%）。在1500 K退火后，Cu0.85Pt0.15和Ag0.05Au0.05Cu0.8Pt0.05Pd0.05等组分的活性分别比Cu（111）和等摩尔HEAs高~ 5倍和~ 10倍。经过dft验证的分析发现了一个可转移的局部基序——嵌入富cu的第一和第二相邻壳中的cu -顶部位点——它将*CO结合向火山最佳方向调整，并使富cu活动脊合理化。将“高熵”作为一种设计策略，而不是严格的组成规则，提供了实验上可访问的组成窗口和退火条件，以及优化多组分合金电催化剂的可重用工作流程。

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引用次数: 0

Zeolite subcrystal-induced formation of short and curved NiMoS2 slabs toward highly efficient hydrodesulfurization 沸石亚晶诱导短弯NiMoS2板的形成及高效加氢脱硫

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-05 DOI: 10.1016/j.jcat.2026.116672

Wanyi Li , Wenbiao Zhang , He Li , Yi Tang , Yahong Zhang

Molybdenum disulfide (MoS₂) holds promise in catalysis due to its edge-confined activity, but its structural rigidity and strong in-plane Mo-S bonding limit the exposure of active sites. Herein, we propose a high-curvature support-induced method using ultrasmall ZSM-5 subcrystals (Z-5-SC) to tailor the formation of NiMoS₂ on them. The high curvature and abundant external silanol groups of Z-5-SC induce tensile strain and strong interfacial anchoring, generating short and curved NiMoS₂ slabs with enhanced sulfur vacancies and Ni-Mo-S phase formation. Compared to nanocrystalline zeolite supports, the NiMoS₂/Z-5-SC exhibits 7.3-fold higher hydrodesulfurization (HDS) activity toward 4,6-dimethyldibenzothiophene (k_HDS = 0.624 h⁻¹), rapid hydrodenitrogenation (HDN) response with minimized HDS suppression in simultaneous HDS and HDN reactions, and excellent cycling stability over 15 cycles. This work presents an effective curvature-engineering strategy to enhance the catalytic potential of MoS₂, offering new insights into the design of engineered two-dimensional materials for hydrotreating and beyond.

二硫化钼（MoS2）由于其边缘受限的活性而在催化方面具有广阔的前景，但其结构刚性和强的平面内Mo-S键限制了活性位点的暴露。在此，我们提出了一种高曲率的支持诱导方法，使用超小型ZSM-5亚晶体（Z-5-SC）来定制NiMoS2的形成。Z-5-SC的高曲率和丰富的外部硅醇基团诱导拉伸应变和强界面锚定，形成短而弯曲的NiMoS2板，增加了硫空位和Ni-Mo-S相的形成。与纳米沸石载体相比，NiMoS2/Z-5-SC对4,6-二甲基二苯并噻吩的加氢脱硫（HDS）活性高7.3倍（kHDS = 0.624 h−1），加氢脱氮（HDN）反应迅速，同时HDS和HDN反应对HDS的抑制最小，并且在15个循环内具有良好的循环稳定性。这项工作提出了一种有效的曲率工程策略来增强MoS2的催化潜力，为加氢处理等工程二维材料的设计提供了新的见解。

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引用次数: 0

Synergistic catalysis of oxygen vacancy-Cu0 dual-active-site derived from Cu-Zn mineral salt for boosting ethanol dehydrogenation into acetaldehyde 铜锌无机盐衍生氧空位- cu0双活性位点协同催化乙醇脱氢制乙醛

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-05 DOI: 10.1016/j.jcat.2026.116670

Qingwei Meng , Hui Luo , Fucheng Chen , Lungang Chen , Jinliang Song , Xiaorui Du , Yiyuan Zhou , Anqi Wang , Xiaoping Wu , Tiejun Wang

The non-oxidative dehydrogenation of ethanol (EDH) to acetaldehyde represents a promising route for biomass resource utilization. Although Cu/ZnO catalysts are widely employed industrially, their application in EDH remains underexplored. This study investigates the impact of precursor composition—using aurichalcite, zinc malachite, and their mixtures—on the structure and EDH performance of derived Cu/ZnO catalysts. The precursor composition significantly modulates the oxygen vacancy concentration in the catalysts, thereby tuning electronic metal-support (Cu-ZnO) interactions and the relative abundances of Cu⁰ and defective Zn^δ+ species. The aurichalcite-derived catalyst exhibits the smallest Cu particle size, highest oxygen vacancy and Cu⁰ content, facilitating the formation of abundant oxygen vacancy-Cu⁰ dual-active-sites at the Cu-ZnO interface. In situ DRIFTS characterization demonstrate that oxygen vacancies play a critical role in the adsorption of ethanol, and the oxygen vacancy-Cu⁰ dual-active sites facilitate the cleavage of the α-C–H bond, thereby enhancing the rate of ethanol dehydrogenation. Mechanism studies reveal that the oxygen vacancy promotes adsorption via the ethanol C-O or O–H bond, while adjacent metallic Cu⁰&Cu⁺ activates and cleaves the C–H and O–H bonds. This oxygen vacancy-metal dual-active-sites synergistically enhances the intrinsic activity for ethanol dehydrogenation. Furthermore, catalyst with lower acidity and basicity were found to favor acetaldehyde selectivity. The catalyst derived from the mixed-phase precursor demonstrated optimal performance, achieving 63 % ethanol conversion and 90.2 % acetaldehyde selectivity at 270 °C under a WHSV of 1 h⁻¹, with a catalyst lifetime exceeding 230 h. This work provides valuable insights for designing efficient Cu/ZnO catalysts for selective acetaldehyde production via ethanol dehydrogenation.

乙醇（EDH）非氧化脱氢制乙醛是生物质资源利用的一条有前途的途径。虽然Cu/ZnO催化剂在工业上得到了广泛的应用，但其在EDH中的应用仍未得到充分的探索。本研究考察了前驱体组成（金银石、孔雀石锌及其混合物）对衍生Cu/ZnO催化剂结构和EDH性能的影响。前驱体组成显著调节催化剂中的氧空位浓度，从而调节电子金属-载体（Cu-ZnO）相互作用以及Cu0和缺陷Znδ+的相对丰度。该催化剂具有最小的Cu粒度、最高的氧空位和Cu0含量，有利于在Cu- zno界面形成丰富的氧空位-Cu0双活性位点。原位DRIFTS表征表明，氧空位对乙醇的吸附起着关键作用，氧空位- cu0双活性位点有利于α-C-H键的断裂，从而提高乙醇的脱氢速率。机理研究表明，氧空位通过乙醇的C-O或O-H键促进吸附，而相邻的金属Cu⁰&；Cu+激活并切割C-H和O-H键。这种氧空位-金属双活性位点协同提高了乙醇脱氢的固有活性。此外，较低的酸性和碱性催化剂有利于乙醛的选择性。从混合相前驱体衍生的催化剂表现出最佳性能，在270°C下，在1 h−1的WHSV下，实现了63%的乙醇转化率和90.2%的乙醛选择性，催化剂寿命超过230 h。这项工作为设计高效的Cu/ZnO催化剂通过乙醇脱氢选择性生产乙醛提供了有价值的见解。

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引用次数: 0

Pivotal strategies towards stable Ni-based catalysts for dry reforming of methane: resisting carbon accumulation 甲烷干重整稳定镍基催化剂的关键策略：抵抗碳积累

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-05 DOI: 10.1016/j.jcat.2026.116671

Shaoyuan Sun , Dezheng Li , Huimin Liu , Chao Wang , Manqi Zhao , Heting Hou , Yonghua Zhao , Qijian Zhang , Dehua He , Yiming Lei

Catalytic dry reforming of methane (DRM) can convert greenhouse gases (CO₂ and CH₄) into syngas (CO + H₂) so as to be expected to realize carbon neutrality and green energy production. Ni-based catalysts with low cost and high efficiency are promising for DRM field. However, the rapid cracking of CH₄ on Ni surface becomes a double-edged sword, resulting in high efficiency and undesired carbon accumulation. To improve the anti-carbon accumulation ability, the catalytic communities have proposed effective strategies, represented by i) regulation and stabilization of small metal nanoparticles, ii) regulation of the support improving oxidation of deposited carbon. Herein, we highlight their effects in enhancing anti-carbon accumulation ability and discuss their anti-carbon accumulation abilities under realistic DRM reaction conditions, aiming at inspiring more interesting studies toward DRM and even the whole catalytic field.

甲烷催化干重整（DRM）可以将温室气体（CO2和CH4）转化为合成气（CO + H2），有望实现碳中和和绿色能源生产。低成本、高效率的镍基催化剂在DRM领域具有广阔的应用前景。然而，CH4在Ni表面的快速裂解是一把双刃剑，导致了高效率和不希望的碳积累。为了提高抗碳积累能力，催化群落提出了有效的策略，即i)调节和稳定小金属纳米颗粒，ii)调节载体促进沉积碳的氧化。本文重点介绍了它们在增强抗碳积累能力方面的作用，并讨论了它们在现实DRM反应条件下的抗碳积累能力，旨在激发对DRM乃至整个催化领域更多有趣的研究。

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引用次数: 0

Promoting the in-situ generation and stabilizing of active β-NiOOH on nickel sulfide nanosheet for superior electrochemical methanol oxidation 促进活性β-NiOOH在硫化镍纳米片上的原位生成和稳定，实现优异的电化学甲醇氧化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-03 DOI: 10.1016/j.jcat.2026.116668

Yu-Nan Yi , Xiao-Dan Guan , Xin-Yu Peng , Xiaobing Shi

NiOOH is regarded as the most active species for selective methanol oxidation reaction (MOR), but the high oxidation energy of NiOOH makes it hard to directly synthesize, except under high anodic polarization. Besides, the high active β-NiOOH is prone to be irreversibly over-oxidized to less active and unstable γ-NiOOH. Herein, we propose a cobalt-mediated strategy to promote the in-situ generation of active β-NiOOH at ultralow applied potential on Ni₃S₂ nanosheets and prevent overoxidation of β-NiOOH to γ-NiOOH during MOR, this promoting effect is confirmed by the in-situ Raman spectroscopy analysis. Furthermore, DFT calculations reveal that substitution of slight Co atoms for Ni atoms in Ni₃S₂ weakens the Ni–S bonds and formation energy of S vacancies, as well as enhancing the *OH adsorption at Ni sites, thereby promoting the in-situ generation and stabilizing of β-NiOOH. Consequently, the optimal Ni_2.94Co_0.06S₂@NF catalyst exhibts superior MOR performance, with a potential of 1.41 V vs. RHE at 100 mA cm⁻² and above 97 % of FE_formate at ∼300 mA cm⁻². This study provides a deep insight into modulating surface reconstruction of Ni-based nanocatalyst to promote in-situ generating of real and robust active site for MOR and other nucleophile oxidation reactions.

NiOOH被认为是甲醇选择性氧化反应（MOR）中最活跃的物质，但NiOOH的高氧化能使得它很难直接合成，除非在高阳极极化条件下。此外，高活性的β-NiOOH容易被不可逆过氧化生成活性较低且不稳定的γ-NiOOH。在此，我们提出了一种钴介导的策略，以促进Ni3S2纳米片在超低电位下原位生成活性β-NiOOH，并防止β-NiOOH在MOR过程中过度氧化为γ-NiOOH，这种促进作用通过原位拉曼光谱分析得到证实。此外，DFT计算表明，Ni3S2中少量的Co原子取代Ni原子削弱了Ni - S键和S空位的形成能，增强了Ni位点对*OH的吸附，从而促进了β-NiOOH的原位生成和稳定。因此，最优Ni2.94Co0.06S2@NF催化剂表现出优异的MOR性能，在100 mA cm - 2时与RHE的电位为1.41 V，在~ 300 mA cm - 2时与fe甲酸的电位超过97%。该研究为调控镍基纳米催化剂的表面重构以促进MOR等亲核试剂氧化反应的原位生成真实而稳健的活性位点提供了深入的见解。

{"title":"Promoting the in-situ generation and stabilizing of active β-NiOOH on nickel sulfide nanosheet for superior electrochemical methanol oxidation","authors":"Yu-Nan Yi , Xiao-Dan Guan , Xin-Yu Peng , Xiaobing Shi","doi":"10.1016/j.jcat.2026.116668","DOIUrl":"10.1016/j.jcat.2026.116668","url":null,"abstract":"<div><div>NiOOH is regarded as the most active species for selective methanol oxidation reaction (MOR), but the high oxidation energy of NiOOH makes it hard to directly synthesize, except under high anodic polarization. Besides, the high active β-NiOOH is prone to be irreversibly over-oxidized to less active and unstable γ-NiOOH. Herein, we propose a cobalt-mediated strategy to promote the <em>in-situ</em> generation of active β-NiOOH at ultralow applied potential on Ni<sub>3</sub>S<sub>2</sub> nanosheets and prevent overoxidation of β-NiOOH to γ-NiOOH during MOR, this promoting effect is confirmed by the <em>in-situ</em> Raman spectroscopy analysis. Furthermore, DFT calculations reveal that substitution of slight Co atoms for Ni atoms in Ni<sub>3</sub>S<sub>2</sub> weakens the Ni–S bonds and formation energy of S vacancies, as well as enhancing the *OH adsorption at Ni sites, thereby promoting the <em>in-situ</em> generation and stabilizing of β-NiOOH. Consequently, the optimal Ni<sub>2.94</sub>Co<sub>0.06</sub>S<sub>2</sub>@NF catalyst exhibts superior MOR performance, with a potential of 1.41 V vs. RHE at 100 mA cm<sup>−2</sup> and above 97 % of <em>FE</em><sub>formate</sub> at ∼300 mA cm<sup>−2</sup>. This study provides a deep insight into modulating surface reconstruction of Ni-based nanocatalyst to promote <em>in-situ</em> generating of real and robust active site for MOR and other nucleophile oxidation reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116668"},"PeriodicalIF":6.5,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895292","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

Optimal photosynthesis of 1O2 via energy transfer over linker-engineered cyclooctatetrathiophene-based porous aromatic frameworks 通过连接剂工程环四噻吩基多孔芳香框架的能量转移实现1O2的最佳光合作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-02 DOI: 10.1016/j.jcat.2026.116667

Linzhu Cao , Tianye Gao , Tianyu Qiu , Xin Tao

Precisely tuning the excitonic effect of porous organic semiconductors is essential to achieve efficient photosynthesis of singlet oxygen (¹O₂) from ground state oxygen (³O₂) via energy transfer pathway. In this study, a linkage engineering strategy is proposed to tune the excitonic effect of cyclooctatetrathiophene-based porous organic semiconductor photocatalysts. It is found that altering linear linkers significantly influence the excitonic effect of these semiconductors. Notably, the highly twisted dimethylfluorene-linked COTh-based polymeric system possesses higher exciton binding energy and improved intersystem crossing (ISC) efficiency, which are favorable for photoinduced ¹O₂ generation through energy transfer pathway. PAF-374 achieved a record-high ¹O₂ generation rate (133.8 μM min⁻¹) with 98 % selectivity in aerobic photocatalytic system when using furfuryl alcohol as probe. This unique performance enables potential applications for photocatalytic drug synthesis (modafinil and artemisinin) and wastewater treatment over this photocatalyst system. In addition, a detailed structure–property correlation is revealed by theoretical calculations.

精确调节多孔有机半导体的激子效应是实现单线态氧（1O2）与基态氧（3O2）通过能量转移途径进行高效光合作用的关键。在这项研究中，提出了一种链接工程策略来调节环四噻吩基多孔有机半导体光催化剂的激子效应。研究发现，改变线性连接对这些半导体的激子效应有显著影响。值得注意的是，高扭曲的二甲基芴连接的coth基聚合物体系具有更高的激子结合能和更高的系统间交叉（ISC）效率，这有利于通过能量传递途径产生光诱导的1O2。PAF-374在以糠醇为探针的好氧光催化体系中获得了创纪录的10o2生成率（133.8 μM min−1）和98%的选择性。这种独特的性能使得光催化药物合成（莫达非尼和青蒿素）和废水处理具有潜在的应用前景。此外，通过理论计算揭示了详细的结构-性能关系。

{"title":"Optimal photosynthesis of 1O2 via energy transfer over linker-engineered cyclooctatetrathiophene-based porous aromatic frameworks","authors":"Linzhu Cao , Tianye Gao , Tianyu Qiu , Xin Tao","doi":"10.1016/j.jcat.2026.116667","DOIUrl":"10.1016/j.jcat.2026.116667","url":null,"abstract":"<div><div>Precisely tuning the excitonic effect of porous organic semiconductors is essential to achieve efficient photosynthesis of singlet oxygen (<sup>1</sup>O<sub>2</sub>) from ground state oxygen (<sup>3</sup>O<sub>2</sub>) via energy transfer pathway. In this study, a linkage engineering strategy is proposed to tune the excitonic effect of cyclooctatetrathiophene-based porous organic semiconductor photocatalysts. It is found that altering linear linkers significantly influence the excitonic effect of these semiconductors. Notably, the highly twisted dimethylfluorene-linked COTh-based polymeric system possesses higher exciton binding energy and improved intersystem crossing (ISC) efficiency, which are favorable for photoinduced <sup>1</sup>O<sub>2</sub> generation through energy transfer pathway. PAF-374 achieved a record-high <sup>1</sup>O<sub>2</sub> generation rate (133.8 μM min<sup>−1</sup>) with 98 % selectivity in aerobic photocatalytic system when using furfuryl alcohol as probe. This unique performance enables potential applications for photocatalytic drug synthesis (modafinil and artemisinin) and wastewater treatment over this photocatalyst system. In addition, a detailed structure–property correlation is revealed by theoretical calculations.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116667"},"PeriodicalIF":6.5,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895312","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

Theoretical investigation of decomposition and hydrolysis of sulfonamides on CeO2(111) 磺胺类化合物在CeO2（111）上分解水解的理论研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-31 DOI: 10.1016/j.jcat.2025.116663

Ye Xu , Timm McNeese

Sulfonamides are a group of synthetic compounds widely used in human and veterinarian medicine (a.k.a. sulfa drugs) and can accumulate in the environment. We show theoretically that ceria can catalyze the hydrolysis of sulfonamides via S − N bond scission over a pair of Ce-O lattice sites, where O_latt attacks the S center and displaces the N center in a nucleophilic substitution, yielding a primary amine and a sulfonic acid as products. Our calculations shed light on how different substituents on the S and N centers affect S − N bond scission by comparing non-aromatic vs. aromatic groups, homo- vs. heterocyclic aromaticity, and further functionalization of the aromatic groups. Stabilizing the S and N centers is found to have the opposite effects on the facility of S -− N bond scission. The desorption of sulfonic acid is strongly endothermic in the gas phase but is calculated to be facilitated by solvation effects when sulfonic acid undergoes acid-base titration with the amine product to form an oxyanion and a pyridinium cation, or when it self-ionizes to a zwitterion.

磺胺类化合物是一类广泛用于人体和兽药的合成化合物（又称磺胺类药物），可在环境中积累。我们从理论上证明，铈可以通过S − 在一对Ce-O晶格位点上的N键断裂来催化磺胺类化合物的水解，其中Olatt攻击S中心并在亲核取代中取代N中心，生成伯胺和磺酸作为产物。我们的计算通过比较非芳香族和芳香族基团、同环和杂环芳香族基团的芳香性以及芳香族基团的进一步功能化，揭示了S和N中心不同取代基对S − N键断裂的影响。研究发现，稳定S和N中心对S-N键断裂的能力有相反的影响。磺酸的脱附在气相中是强吸热的，但计算出，当磺酸与胺产物进行酸碱滴定形成氧阴离子和吡啶阳离子，或自电离成两性离子时，溶剂化效应会促进脱附。

引用次数: 0

Enhanced charge transfer and oxygen vacancies by interface engineering for CO2 reforming of toluene 界面工程增强电荷转移和氧空位在甲苯CO2重整中的应用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-31 DOI: 10.1016/j.jcat.2025.116665

Yongqi Kuang , Jiawen Ma , Sibudjing Kawi , Shuzhuang Sun , Yuqianer Zeng , Lina Liu

CO₂ reforming of tar reaction (CRT) is a promising method for simultaneous removal and conversion of CO₂ and tar in syngas from the biomass gasification technology, which is essential for utilization and upgrading of syngas. However, the deactivation of supported Ni catalysts by sintering and carbon deposits remains the most challenging issue. In this study, (Mg, Al, Ce)O_x nanosheet-supported Ni-based catalysts with varying Ce/Ni ratios (0, 0.1, 0.2, 0.3) were constructed from freeze-dried Ni–Ce–Mg–Al LDH precursors with the thermally dried Ni–Ce_0.2–Mg–Al LDH as a reference. The result suggested that freeze drying favored the achievement of loose nanosheets and highly dispersed metals. With the optimized Ce dosage (Ce/Ni = 0.2), the Ni–Ce_0.2–F–R catalyst exhibited the most superior activity and stability over 40h time-on-stream. The possible reason is that Ni–Ce_0.2–F–R catalyst possessed abundant and homogeneously distributed Ni–CeO₂ interface, which accelerated the electron transfer from CeO₂ to Ni via Ni–O_v–Ce structure (Ov, oxygen vacancy). An electron-rich state of Ni was thus achieved, which could effectively activate the C–H and C–C bonds. Furthermore, the abundant oxygen defects and stronger alkaline sites of the CeO₂ support promoted the adsorption and activation of CO₂, which was conducive to the elimination of coke adjacent Ni metal sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) suggested that the abundant surface-active oxygen species facilitated the deep oxidation and ring opening of the benzene ring.

CO2重整焦油反应（CRT）是生物质气化技术中合成气中CO2和焦油同时脱除和转化的一种有前景的方法，对合成气的利用和升级至关重要。然而，通过烧结和积碳使负载型镍催化剂失活仍然是最具挑战性的问题。在本研究中，以Ni- ce0.2 - Mg - Al LDH为参考，以冷冻干燥的Ni- Ce - Ce - Al LDH为前驱体，构建了不同Ce/Ni比率（0、0.1、0.2、0.3）的（Mg, Al, Ce）Ox纳米片负载的Ni基催化剂。结果表明，冷冻干燥有利于获得松散的纳米片和高度分散的金属。当Ce/Ni = 0.2时，Ni - ce0.2 - f - r催化剂在40h的反应时间内表现出最优的活性和稳定性。可能的原因是Ni - ce0.2 - f - r催化剂具有丰富且分布均匀的Ni - CeO2界面，通过Ni - Ov - ce结构（Ov，氧空位）加速了电子从CeO2向Ni的转移。镍的富电子态可以有效地激活C-H和C-C键。此外，CeO2载体丰富的氧缺陷和较强的碱性位点促进了CO2的吸附和活化，有利于消除邻近Ni金属位点的焦炭。原位漫反射红外傅里叶变换光谱（DRIFTS）表明，丰富的表面活性氧促进了苯环的深度氧化和开环。

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引用次数: 0

Ferroelectric polarization switching regulates single-atom catalysis for water splitting 铁电极化开关调节单原子水裂解催化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-31 DOI: 10.1016/j.jcat.2025.116664

Jiali Wang , Jiajun Lu , Xiuwen Zhao , Guichao Hu , Xiaobo Yuan , Junfeng Ren , Siyun Qi

Dynamic control of catalytic activity remains a major challenge for conventional single-atom catalysts (SACs) whose coordination environments are fixed after construction. In this work, CuInP₂S₆ (CIPS) was employed as a model ferroelectric support to explore how polarization switching modulates catalytic behavior in transition metal single atoms (TM@CIPS) for hydrogen and oxygen evolution reactions (HER and OER). Fifteen transition metals across the 3d-5d series were examined under two polarization states to evaluate the stability and catalytic properties. Polarization switching between upward and downward states was found to dynamically tune catalytic activity, markedly reducing OER overpotentials in systems such as Co@CIPS and Pt@CIPS by optimizing reaction pathways. This enhancement originated from polarization-induced redistribution of interfacial charge, which shifted the d-band center and modified TM-O bonding strength, thereby governing adsorption and reaction energetics. These results establish ferroelectric polarization as an effective strategy for real-time control of catalytic processes and provide fundamental insight for designing next-generation catalysts.

传统单原子催化剂的配位环境是固定的，催化活性的动态控制一直是其面临的主要挑战。在这项工作中，我们以CuInP2S6 （CIPS）作为模型铁电载体，探索极化开关如何调节过渡金属单原子（TM@CIPS）中析氢和析氧反应（HER和OER）的催化行为。研究了3d-5d系列的15种过渡金属在两种极化状态下的稳定性和催化性能。研究发现，在上下状态之间的极化切换可以动态调节催化活性，通过优化反应途径，显著降低Co@CIPS和Pt@CIPS等体系中的OER过电位。这种增强源于极化引起的界面电荷重分布，改变了d带中心，改变了TM-O键的强度，从而控制了吸附和反应的能量学。这些结果确立了铁电极化作为实时控制催化过程的有效策略，并为设计下一代催化剂提供了基础见解。

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引用次数: 0

Atomistic visualization of formaldehyde degradation on the ZnO surface through a Mars-van Krevelen mechanism 通过Mars-van Krevelen机制对氧化锌表面甲醛降解的原子可视化研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-30 DOI: 10.1016/j.jcat.2025.116662

Dan Wang , Youxi Wang , Qingqing Wang , Xiaolin Tan , Zhe Li , Xuefeng Cui , Shijing Tan , Zhenyu Li , Bing Wang , Xiang Shao

Semiconductor oxide-based heterogeneous catalysis and/or photocatalysis provide pivotal solutions to global energy and environmental crises, yet a fundamental understanding of their atomic-level mechanisms lags far behind the practical applications. A typical example is the degradation of formaldehyde (FA) on ZnO surfaces. Although ZnO is extensively employed in sensing and removing FA from the atmosphere, the atomic-level reaction mechanisms remain unclear. Here, we combine scanning tunneling microscopy (STM), temperature-programmed desorption (TPD) measurements, and density functional theory (DFT) calculations to reveal the reaction process of FA on a ZnO(

10 \bar{1} 0

) single-crystalline surface. We directly visualize two competing pathways: dissociation versus dimerization, with dimerization getting significantly accelerated upon ultraviolet (UV) irradiation at room temperature (RT). Furthermore, at elevated temperatures, intermediates react aggressively with surface lattice oxygen, generating abundant oxygen vacancies–a discovery that fundamentally advances our understanding of the Mars-van Krevelen mechanism for FA and similar organics on ZnO. These atomic-level insights open new avenues for designing highly efficient, environment friendly photocatalytic systems based on the semiconducting oxide materials.

基于半导体氧化物的多相催化和/或光催化为全球能源和环境危机提供了关键的解决方案，但对其原子水平机制的基本理解远远落后于实际应用。一个典型的例子是氧化锌表面甲醛的降解。虽然ZnO被广泛应用于大气中FA的传感和去除，但其原子水平的反应机制尚不清楚。在这里，我们结合扫描隧道显微镜（STM）、程序升温解吸（TPD）测量和密度泛函理论（DFT）计算揭示了FA在ZnO（101¯0）单晶表面上的反应过程。我们直接看到两个竞争的途径：解离与二聚化，二聚化在室温（RT）紫外线照射下显着加速。此外，在高温下，中间体与表面晶格氧发生剧烈反应，产生大量的氧空位——这一发现从根本上推进了我们对氧化锌上FA和类似有机物的Mars-van Krevelen机制的理解。这些原子级的见解为设计基于半导体氧化物材料的高效、环境友好型光催化系统开辟了新的途径。

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引用次数: 0