Journal of Catalysis最新文献_第4页

Protonation-enhanced H2O2 electrosynthesis: high-selectivity and high-yield with a noble-metal-free CTF/BHN composite 质子增强H2O2电合成：无贵金属CTF/BHN复合材料的高选择性和高产率

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-05 DOI: 10.1016/j.jcat.2025.116616

Fengyi Wang, Hong Li, Shenshen Zhang, Bin Duan, Niu Huang, Yong Zheng, Binbin Jia, Siran Xu, Wei Liu, Liqun Ye

The development of non-noble metal catalysts with high activity and selectivity is critical for the electrocatalytic production of hydrogen peroxide (H₂O₂). Herein, we report a composite catalyst (CTF/BHN) fabricated by chelating a basic bismuth salt (BHN) with a bipyridine-containing covalent triazine framework (CTF), forming strong Bi-bipyridine bonds at the interface. This catalyst exhibits exceptional H₂O₂ selectivity (92–98 %) over a wide potential range (0.3–0.62 V vs. RHE). In H-type cell tests, it achieves a Faraday efficiency of 88.9 % at 20 mA cm⁻², with a high H₂O₂ production rate of 1.65 mol g⁻¹h⁻¹, and maintains stable performance for 42 h. In-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and X-ray photoelectron spectroscopy (XPS) reveal that the superior performance stems from synergistic interfacial effects: electron transfer from BHN to CTF enhances charge transport, while polarized interfaces promote water dissociation and protonation of pyridine groups in CTF to form Py*H intermediates. Py*H acts as a proton relay, facilitating the protonation of adsorbed *O₂ to *OOH at Bi active sites. Concurrently, the enhanced interaction between *OOH and the catalyst surface (evidenced by the blue-shifted *OOH peak) stabilizes *OOH and suppresses its dissociation, thereby driving the 2e⁻ ORR pathway for efficient H₂O₂ generation.

开发具有高活性和选择性的非贵金属催化剂是电催化生产过氧化氢（H2O2）的关键。在此，我们报道了一种复合催化剂（CTF/BHN），它是由碱式铋盐（BHN）与含联吡啶的共价三嗪框架（CTF）螯合制备的，在界面处形成强的双联吡啶键。该催化剂在较宽的电位范围内（0.3-0.62 V vs. RHE）表现出优异的H2O2选择性（92 - 98%）。在h型电池测试中，在20 mA cm−2条件下，其法拉第效率达到88.9%，H2O2产率高达1.65 mol g−1h−1，并保持42 h的稳定性能。原位衰减全反射表面增强红外吸收光谱（ATR-SEIRAS）和x射线光电子能谱（XPS）表明，优越的性能源于协同界面效应。从BHN到CTF的电子转移增强了电荷输运，而极化界面促进CTF中的水解离和吡啶基团质子化形成Py*H中间体。Py*H充当质子继电器，促进吸附在Bi活性位点的*O2质子化成*OOH。同时，*OOH与催化剂表面的相互作用增强（由*OOH峰的蓝移证明），稳定*OOH并抑制其解离，从而驱动2e - ORR途径高效生成H2O2。

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引用次数: 0

Iron dual-atom sites for high-efficiency CO2 electroreduction at industrial-level current density 铁双原子位在工业水平电流密度下的高效CO2电还原

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-05 DOI: 10.1016/j.jcat.2025.116617

Peng Zhang , Linglong Wang , Jiansong Miao , Tao Gan , Bangyan Zhang , Guanna Li , Chunming Xu , Xiaohui Sun

Dual-atom catalysts (DACs) with unique interactions between neighboring sites are promising candidates in the electrocatalytic CO₂ reduction reaction (CO₂RR). Yet, the controlled synthesis of pure DACs remains a challenge to date. Herein, we propose a facile cation–anion pair adsorption-pyrolysis approach to fabricate a nitrogen-doped carbon supported Fe DAC. Based on this strategy, Fe₂ pairs can be homogeneously incorporated into the carbon substrate. When this candidate was evaluated in the electrocatalytic CO₂RR, it exhibited a CO faradaic efficiency (FE_CO) of ∼97 % at an industrial current density of 200 mA cm⁻² in a gas diffusion electrode (GDE)-based flow cell filled with 0.5 M KHCO₃ electrolyte, surpassing most of the reported Fe based SACs. Experiments combined with theory revealed that the Fe₂ pair with enhanced electronic localization lowered the reaction free energy for COOH* formation on Fe, thereby boosting the catalytic performance in CO₂RR. The structure–property relationship built in this study offers atomic-level insights into the rational design of electrocatalysts for efficient CO₂RR, and extends the application of DACs for heterogeneous electrocatalysis and beyond.

双原子催化剂（DACs）在CO2电催化还原反应（CO2RR）中具有独特的相互作用。然而，控制纯dac的合成至今仍是一个挑战。在此，我们提出了一种易阳离子-阴离子对吸附-热解方法来制备氮掺杂碳负载的铁DAC。基于这种策略，Fe2对可以均匀地结合到碳衬底中。当该候选物在电催化CO2RR中进行评估时，在充满0.5 M KHCO3电解质的气体扩散电极（GDE）流电池中，在工业电流密度为200 mA cm - 2的情况下，其CO法拉第效率（FECO）为~ 97 %，超过了大多数报道的Fe基SACs。实验与理论结合表明，电子定位增强的Fe2对降低了Fe上生成COOH*的反应自由能，从而提高了CO2RR中的催化性能。本研究建立的结构-性能关系为高效CO2RR电催化剂的合理设计提供了原子水平的见解，并扩展了dac在多相电催化及其他领域的应用。

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引用次数: 0

Al3+-induced ferromagnetic coupling in NiFe LDH for magnetic field-enhanced oxygen evolution reaction 磁场增强析氧反应中Al3+诱导的NiFe LDH铁磁偶联

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-05 DOI: 10.1016/j.jcat.2025.116615

Keyi Lv, Bo Feng, Ziyong Zhang, Nianwen Song, Xiangwen Tan, Yanfei Wei, Ziyang Yan, Yuchao Zhang, Xiaofei Yu, Lanlan Li, Xinghua Zhang, Xiaojing Yang, Zunming Lu

The oxygen evolution reaction (OER) has been identified as a bottleneck in the water splitting process. The OER process is defined by the transformation of oxygen from the diamagnetic singlet state of OH⁻ or H₂O to the paramagnetic triplet state of O₂. This work proposes a theoretical model describing the electronic states of Ni sites in NiFeAl LDH, where the incorporation of Al³⁺ modulates the local electronic environment and strengthens the ferromagnetic exchange interactions between Ni²⁺-O-Ni³⁺ units. This modulation drives a magnetic evolution from an antiferromagnetic to a ferromagnetic configuration. Both experimental and theoretical results demonstrate that the OER activity of NiFeAl LDH catalysts is strongly affected by magnetic field conditions. Density functional theory (DFT) calculations reveal that the magnetic field enhances the spin polarization of Ni centers, leading to more favorable reaction thermodynamics and promoting spin-selective electron transfer pathways. This study provides a new theoretical perspective on the coupling between magnetic fields and spin configurations, thereby deepening the understanding of spin-dependent catalytic processes and offering a novel direction for the development of high-performance magnetic-sensitive catalysts.

析氧反应（OER）已被认为是水裂解过程中的瓶颈。OER过程的定义是氧从OH−或H2O的反磁性单线态转变为O2的顺磁性三重态。本研究提出了一个描述NiFeAl LDH中Ni位电子态的理论模型，其中Al3+的加入调节了局部电子环境并加强了Ni2+-O-Ni3+单元之间的铁磁交换相互作用。这种调制驱动从反铁磁到铁磁结构的磁演化。实验和理论结果均表明，NiFeAl LDH催化剂的OER活性受磁场条件的强烈影响。密度泛函理论（DFT）计算表明，磁场增强了Ni中心的自旋极化，导致更有利的反应热力学和促进自旋选择性电子转移途径。本研究为研究磁场与自旋构型之间的耦合提供了新的理论视角，从而加深了对自旋依赖催化过程的认识，为高性能磁敏催化剂的开发提供了新的方向。

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引用次数: 0

Electronic and geometric structure engineered copper sites enhance *CO and *OH co-adsorption for CO2 electroreduction to C2+ products 电子和几何结构工程铜位点增强了CO和OH的共吸附，使CO2电还原为C2+产物

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-04 DOI: 10.1016/j.jcat.2025.116614

Hui Fan , Jia-Ao Huang , Xia-Guang Zhang , Yan-Bo Hua , Yuan-Hao Li , Kun Jiang , Hong Li , Tian-Wen Jiang , Wen-Bin Cai

Oxide-derived copper (OD-Cu) is one of the state-of-the-art catalysts for electrochemical carbon dioxide reduction reaction (CO₂RR) to multi-carbon (C₂₊) products, but it generally suffers from the active site degradations during reconstruction. Herein, we propose an integrative strategy to simultaneously modulate electronic and geometric structure of Cu active sites, i.e., the valence state and coordination environment. By employing a dual-valence Cu (DV-Cu) oxysalt as the precursor, we constructed a reduced DV-Cu (RDV-Cu) catalyst, which features abundant Cu^δ+ and undercoordinated Cu species, representing electronic and geometric structure engineered active sites, respectively. Comprehensive characterizations reveal that, compared to Cu₂O-derived RCu₂O, RDV-Cu not only preserves a higher concentration of electronically active Cu^δ+ species but also introduces more geometrically active undercoordinated Cu sites. Benefiting from these structural advantages, RDV-Cu achieves a maximum Faradaic efficiency for C₂₊ products of 72.3 % at –1.1 V in an H-cell, and 82.8 % at −400 mA cm⁻² in a flow cell, significantly outperforming RCu₂O. In situ vibrational spectroscopic studies disclose a high surface coverage of *CO and *OH induced by the Cu^δ+ and undercoordinated in RDV-Cu, which enhances the C–C coupling reaction. This work proposes a new strategy for fabricating high-performance OD-Cu catalysts and reveals a structure-adsorbate-performance relationship for promoting the formation of C₂₊ products.

氧化物衍生铜（OD-Cu）是电化学二氧化碳还原反应（CO2RR）生成多碳（C2+）产物的催化剂之一，但在重构过程中存在活性位点降解的问题。在此，我们提出了一种综合策略，同时调制铜活性位点的电子和几何结构，即价态和配位环境。以双价Cu （DV-Cu）氧盐为前驱体，构建了一种还原型DV-Cu （RDV-Cu）催化剂，该催化剂具有丰富的Cuδ+和欠配位Cu，分别代表电子和几何结构工程活性位点。综合表征表明，与cu20衍生的RCu2O相比，RDV-Cu不仅保留了更高浓度的电子活性Cuδ+，而且引入了更多几何活性的欠配位Cu位点。得益于这些结构优势，RDV-Cu在h型电池中，当电压为-1.1 V时，C2+产物的最大Faradaic效率为72.3 %，在流型电池中，当电压为400 mA·cm−2时，Faradaic效率为82.8 %，显著优于RCu2O。原位振动光谱研究表明，在RDV-Cu中Cuδ+和欠配位诱导*CO和*OH的高表面覆盖率，增强了C-C偶联反应。本研究提出了一种制备高性能OD-Cu催化剂的新策略，揭示了促进C2+产物形成的结构-吸附-性能关系。

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引用次数: 0

Mechanistic investigations on benzaldehyde hydrogenation on Cu electrocatalyst: the role of local solvent environment 苯甲醛在Cu电催化剂上加氢的机理研究：局部溶剂环境的作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-04 DOI: 10.1016/j.jcat.2025.116611

Chong-Hui Jiang , Hao Cao , Qing-Yang Liu , Zhen Yao , Wei Lin , Yang-Gang Wang

Electrocatalytic hydrogenation of aromatic aldehydes represents a promising route for valorizing biomass-derived feedstocks. However, achieving efficient and selective aldehyde hydrogenation remains challenging, due in part to an insufficient understanding of reaction mechanisms under operational conditions. In this study, we reveal a strong correlation between electrochemical hydrogenation performance and the local solvent environment. We show that a hydrophilic region near the carbonyl oxygen facilitates hydrogenation via the Eley–Rideal (ER) mechanism, wherein solvent water molecules participate directly in the reaction. In contrast, a hydrophobic interface characterized by a rigid hydrogen-bond network suppresses ER-based hydrogenation at the carbon site. Only when the hydrogen-bond network becomes looser can carbon hydrogenation via the ER pathway be activated. These mechanistic insights clarify how the solvent environment dictates the electrocatalytic hydrogenation of aromatic aldehydes, pointing toward a viable strategy of tuning the solvent microenvironment to enhance electrocatalytic selectivity in biomass upgrading.

电催化加氢芳香族醛代表了生物质衍生原料的一个有前途的途径。然而，实现高效和选择性的醛加氢仍然具有挑战性，部分原因是对操作条件下的反应机制了解不足。在这项研究中，我们揭示了电化学加氢性能与局部溶剂环境之间的强烈相关性。我们发现羰基氧附近的亲水性区域通过埃利-理想（ER）机制促进氢化，其中溶剂水分子直接参与反应。相反，以刚性氢键网络为特征的疏水界面抑制了碳位点的er基氢化。只有当氢键网络变得更松散时，才能激活内质网途径的碳加氢。这些机制的见解阐明了溶剂环境如何决定芳香醛的电催化加氢，指出了调整溶剂微环境以提高生物质升级电催化选择性的可行策略。

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引用次数: 0

PFOA catalytic reaction mechanisms on zerovalent iron (Fe0): A DFT investigation PFOA对零价铁（Fe0）的催化反应机理：DFT研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-03 DOI: 10.1016/j.jcat.2025.116604

Mohamed S. Mohamed , Brian P. Chaplin , Ahmed A. Abokifa

In this study, density functional theory (DFT) calculations with dispersion corrections are employed to investigate catalytic reactions of perfluorooctanoic acid (PFOA) onto zerovalent iron (Fe⁰). The main goal of this investigation is to explain the reaction mechanisms, including bond dissociation energies, activation barriers, and rate-determining steps (RDSs), of PFOA degradation. Additionally, we aim to reveal the catalytic effects of Fe⁰ by comparing the reaction energy profile for the degradation of PFOA both in solution (i.e., isolated) and after adsorption on Fe⁰. Along with investigating previously reported pathways, this study proposes a new PFOA degradation pathway on Fe⁰. Overall, the results revealed that Fe⁰ plays a key role in the catalytic degradation of PFOA, significantly affecting the RDSs and increasing defluorination rates. For instance, the activation barrier for the decarboxylation step significantly decreased from 3.08 eV to 1.11 eV over the Fe⁰ surface, while the activation barrier for F dissociation decreased from ∼5 eV to 0.54 eV. Additionally, the proposed pathway in this study (i.e., successive defluorination) was found to be the most favorable pathway for PFOA degradation on Fe⁰. Taken together, the DFT results are consistent with reported experimental findings and provide critical insights that will help advance the design of catalysts for PFAS degradation.

在本研究中，采用密度泛函理论（DFT）计算与分散校正来研究全氟辛酸（PFOA）与零价铁（Fe0）的催化反应。本研究的主要目的是解释PFOA降解的反应机制，包括键解离能、激活障碍和速率决定步骤（rds）。此外，我们的目的是通过比较Fe0在溶液（即分离）和吸附后的反应能谱来揭示Fe0对PFOA降解的催化作用。在对已有报道的降解途径进行研究的基础上，本研究提出了一种新的PFOA在Fe0上降解途径。综上所述，Fe0在PFOA的催化降解中起着关键作用，显著影响rds并提高脱氟率。例如，在Fe0表面上，脱羧步骤的激活势垒从3.08 eV显著降低到1.11 eV，而F解离的激活势垒从~ 5 eV降低到0.54 eV。此外，本研究提出的途径（即连续脱氟）被发现是Fe0上PFOA降解的最有利途径。综上所述，DFT结果与报道的实验结果一致，并提供了有助于推进PFAS降解催化剂设计的关键见解。

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引用次数: 0

Engineering photocatalytic active centers in covalent organic framework isomers via A/K-region positional isomerization of pyrene for H2O2 production 工程光催化活性中心共价有机框架异构体通过A/ k区位置异构芘生产H2O2

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-02 DOI: 10.1016/j.jcat.2025.116607

Yusen Li , Xiaobin Hou , Xitong Ren , Yajie Tian , Jiajie Sun , Feng Bai

The integration of dual active sites for concurrent oxygen reduction (ORR) and water oxidation (WOR) within a single covalent organic framework (COF) remains a fundamental challenge in the artificial photosynthesis of H₂O₂. To address this, we report a positional isomerization strategy that precisely engineers the substitution sites on a pyrene core, constructing four isomeric pyrene-based COFs (A-Py-COF, KA-Py-COF, AK-Py-COF, and K-Py-COF). Structure-activity studies reveal that K-region substitution is pivotal in activating the framework for efficient stepwise two-electron ORR and two-electron WOR. As a result, the optimized K-Py-COF achieves a remarkable photocatalytic H₂O₂ production rate of 468.3 μmol g^–1h⁻¹ in pure water without sacrificial agents, representing a 7.8-fold enhancement over its A-Py-COF analogue. In a biphasic water-benzyl alcohol system, the H₂O₂ production rate of K-Py-COF increases dramatically by 15.3 times, a performance that surpasses most state-of-the-art metal-free COF photocatalysts. By establishing a clear correlation between molecular isomerism and the localization of redox-active sites, this work provides a novel design principle for developing dual-channel COFs toward sustainable H₂O₂ synthesis.

将同步氧还原（ORR）和水氧化（WOR）的双活性位点整合到一个共价有机框架（COF）中仍然是H2O2人工光合作用的一个基本挑战。为了解决这个问题，我们报道了一种位置异构化策略，该策略精确地设计了芘核心上的取代位点，构建了四种基于芘的异构体COFs （a - py - cof, KA-Py-COF， AK-Py-COF和K-Py-COF）。结构活性研究表明，k区取代是激活有效的双电子ORR和双电子WOR框架的关键。结果表明，优化后的K-Py-COF在无牺牲剂的情况下，光催化H2O2产率达到468.3 μ mol g-1h−1，比a - py - cof提高了7.8倍。在双相水-苯甲醇体系中，K-Py-COF的H2O2产率显著提高了15.3倍，其性能超过了大多数最先进的无金属COF光催化剂。通过建立分子异构与氧化还原活性位点定位之间的明确相关性，本工作为开发双通道COFs以可持续合成H2O2提供了一种新的设计原则。

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引用次数: 0

Selective 1,3-butadiene dimerization to 1,3,7-octatriene catalyzed by a heterogeneous Pd catalyst supported on a sterically encumbered NHC polymer 以空间负担NHC聚合物为载体的非均相钯催化剂催化1,3-丁二烯选择性二聚成1,3,7-辛三烯

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-02 DOI: 10.1016/j.jcat.2025.116612

Yuanyuan Zhu , Yuyong Zhang , Lina Ma , Zhaozhan Wang , Yong Yang

As a significant chemical feedstock, 1,3,7-octatriene (OCT) has so far been synthesized mainly via homogeneous Pd catalyst systems, with no successful application of heterogeneous catalysts reported to date. To overcome the challenges associated with catalyst separation/recovery and the high cost of noble-metal, in this study, we developed a novel heterogeneous catalytic system. Using Scholl coupling method, sterically hindered N-heterocyclic carbene (NHC) ligand was incorporated into a hypercrosslinked polymer network, which served simultaneously as both the catalyst support and the solid ligand in the Pd-catalyzed dimerization of 1,3-butadiene with isopropanol. The heterogenous Pd-supported hypercrosslinked polymer catalyst (denoted as Pd@HCP-NHC-B) was formed in situ during the reaction and demonstrated outstanding catalytic activity. Under optimized conditions, complete conversion of 1,3-butadiene was achieved with a selectivity of up to 93.5% toward the target product OCT, which is comparable to that its homogeneous counterpart. Importantly, the catalyst could be easily separated from the reaction mixture and maintained consistent activity and selectivity over at least 10 consecutive cycles. Characterization studies confirmed that the morphology of the catalyst and the local coordination environment of the metal centers remained unchanged after agglomeration, demonstrating the high stability of the catalyst. This breakthrough paves the way for scalable and industrially feasible heterogeneous catalysts in 1,3-butadiene dimerization.

作为一种重要的化工原料，1,3,7-辛三烯（OCT）的合成目前主要是通过均相钯催化剂体系进行的，尚未见非均相催化剂的成功应用报道。为了克服催化剂分离/回收和贵金属高成本相关的挑战，在本研究中，我们开发了一种新型的多相催化体系。采用Scholl偶联方法，将位阻n -杂环碳（NHC）配体纳入超交联聚合物网络中，在pd催化1,3-丁二烯与异丙醇二聚化反应中同时作为催化剂载体和固体配体。在反应过程中原位生成了多相pd负载的高交联聚合物催化剂（表示为Pd@HCP-NHC-B），并表现出优异的催化活性。在优化条件下，1,3-丁二烯完全转化，对目标产物OCT的选择性高达93.5%，与均相产物相当。重要的是，催化剂可以很容易地从反应混合物中分离出来，并且在至少10个连续循环中保持一致的活性和选择性。表征研究证实，催化剂的形貌和金属中心的局部配位环境在团聚后保持不变，证明了催化剂的高稳定性。这一突破为1,3-丁二烯二聚化的可扩展和工业上可行的多相催化剂铺平了道路。

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引用次数: 0

Machine learning–assisted discovery of chromium bis(2-pyridyl)amine catalysts for ethylene tri-/tetramerization 机器学习辅助发现二（2-吡啶基）铬胺催化乙烯三/四聚化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-02 DOI: 10.1016/j.jcat.2025.116613

Youcai Zhu, Yue Mu, Xiaoke Shi, Shu Yang, Li Sun, Zhen Liu

The selective production of 1-hexene and 1-octene through chromium-catalyzed ethylene oligomerization remains a central challenge in catalyst design. In this work, we developed a fully automated, data-driven workflow to investigate the chromium bis(2-pyridyl)amine (Cr/NNN) catalytic system. A virtual database of 256 ligands with systematically varied R₁-R₃ substituents was constructed, and the relative transition-state Gibbs free energy differences (ΔΔG) between trimerization and tetramerization pathways were computed using DFT. To efficiently represent the key structural and physicochemical characteristics of the catalysts, molecular descriptors were extracted using SMILES-based structure generation combined with xTB calculations and RDKit-derived structural analysis. The developed machine learning models exhibited excellent predictive performance, achieving an R² of 0.90 and a remarkably low MAE of 0.52 kcal/mol. Subsequent SHapley Additive exPlanations (SHAP) analysis identified the key structural features governing ΔΔG, confirming that the selectivity is primarily controlled by local steric effects at R₁, with distant electronic substitutions contributing only weakly. Guided by the machine learning and SHAP analyses, two Cr/NNN catalysts were identified from the DFT-calculated dataset as optimal prototypes, showing exclusive selectivity for 1-hexene and 1-octene formation, respectively. This data-driven strategy can be readily extended to other transition-metal catalytic systems, offering a general framework for accelerating catalyst discovery and selectivity optimization.

通过铬催化乙烯低聚反应选择性生产1-己烯和1-辛烯仍然是催化剂设计中的一个核心挑战。在这项工作中，我们开发了一个全自动的，数据驱动的工作流程来研究铬双（2-吡啶基）胺（Cr/NNN）催化系统。构建了包含256个具有系统变化R1-R3取代基的配体的虚拟数据库，并利用DFT计算了三聚化和四聚化途径之间的相对过渡态吉布斯自由能差（ΔΔG）。为了有效地表达催化剂的关键结构和物理化学特征，使用基于smiles的结构生成结合xTB计算和rdkit衍生的结构分析来提取分子描述符。所开发的机器学习模型具有出色的预测性能，R2为0.90，MAE为0.52 kcal/mol，非常低。随后的SHapley加性解释（SHAP）分析确定了控制ΔΔG的关键结构特征，证实了选择性主要由R1处的局部空间效应控制，远端电子取代的作用很小。在机器学习和SHAP分析的指导下，从dft计算的数据集中确定了两种Cr/NNN催化剂作为最佳原型，分别对1-己烯和1-辛烯的形成具有独家选择性。这种数据驱动的策略可以很容易地扩展到其他过渡金属催化系统，为加速催化剂发现和选择性优化提供了一个总体框架。

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引用次数: 0

A method to reveal the reaction order for reactants in complex electrocatalytic reactions: formic acid/formate oxidation on Au(1 1 1) as the model system 一种揭示复杂电催化反应中反应物反应顺序的方法：甲酸/甲酸在Au（11 11）上氧化为模型体系

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-02 DOI: 10.1016/j.jcat.2025.116608

Zhen Wei , Wei Chen , Meng-Ke Zhang , Li-Guo Cao , Jun Cai , Yan-Xia Chen

Information of reaction orders of respective reactants involved is of great help in unraveling the reaction mechanisms of complex electrocatalytic reactions. However, due to the interactive interferences from potential-dependent (competitive) adsorption of reaction intermediates and spectators as well as mass transfer effect, etc., directly determining the true reaction order of a reactant in electrocatalytic reactions remains challenging. Herein, an effective method for the determination of the genuine reaction order is proposed, illustrated through the case of formic acid/formate oxidation reaction (FAOR) on Au(1 1 1) electrode in solutions of pH = 1.2 and 3.7. The apparent reaction order with respect to formate anion is found to be 1 and 0.5 at the onset potential for FAOR and at higher potentials where the coverage of the HCOO_b spectator reaches saturation, respectively. The validity of reaction order values is verified by kinetic analysis based on the reaction mechanisms with formate as the discharging precursor and the cleavage of C–H bond in HCOO^– as the rate-determining step. Finally, the extension of this method in unveiling the reaction orders in other more complex reactions has been discussed.

有关各反应物反应级数的信息对揭示复杂电催化反应的反应机理有很大帮助。然而，由于反应中间体的电位依赖性（竞争性）吸附、旁观者以及传质效应等相互作用的干扰，直接确定电催化反应中反应物的真实反应顺序仍然是一个挑战。本文通过在pH = 1.2和3.7的溶液中，在Au（1 1 1）电极上进行甲酸/甲酸氧化反应（FAOR）的例子，提出了一种确定真实反应顺序的有效方法。在FAOR的起始电位下，甲酸阴离子的表观反应级数分别为1和0.5，在HCOOb观察者覆盖达到饱和的更高电位下，反应级数分别为1和0.5。以甲酸盐为前驱体，以HCOO -中C-H键裂解为速率决定步骤的反应机理为基础，通过动力学分析验证了反应级数值的有效性。最后，讨论了该方法在揭示更复杂反应阶数方面的推广。

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引用次数: 0