Journal of Catalysis最新文献_第7页

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 : 2026-03-01 Epub 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

A four-component carbonylation reaction of terminal alkynes and arenes toward α, β-unsaturated esters 端炔和芳烃生成α， β-不饱和酯的四组分羰基化反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-21 DOI: 10.1016/j.jcat.2026.116704

Qiangwei Li , Ting Yang , Xiao-Feng Wu

Owing to the high reactivity of the carbon–carbon triple bond, alkynes can react with various reagents to give functionalized alkenes and alkanes, making it a useful compound to build complex molecules. Herein, we reported a one-pot, two-step strategy which use arenes and alkynes as the reactant combined with carbon monoxide to afford α, β-unsaturated esters. The transformation goes through iodonium ions intermediate and proceed under mild conditions, a series of the target products were generated in good to excellent yields.

由于碳碳三键的高反应活性，炔烃可以与各种试剂反应得到功能化的烯烃和烷烃，使其成为构建复杂分子的有用化合物。在此，我们报道了一锅，两步的策略，使用芳烃和炔烃作为反应物与一氧化碳结合得到α， β-不饱和酯。在温和的条件下，通过碘离子中间体进行转化，得到了一系列收率较高的目标产物。

引用次数: 0

Photoredox-catalyzed three-component cyanoalkylation of glycine derivatives: Enabled by dual nitrogen-centered radicals 光氧化还原催化甘氨酸衍生物的三组分氰烷基化：由双氮中心自由基实现

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-13 DOI: 10.1016/j.jcat.2026.116694

Wen-Lin Zou, Zhi Guan, Yan-Hong He

A photoredox-catalyzed three-component reaction has been developed, in which two distinct nitrogen-centered radicals are generated through sequential reductive and oxidative processes mediated by the photocatalyst. This transformation involves C–C bond cleavage and generation of an α‑aminoalkyl radical as parallel key steps, enabling alkene difunctionalization to achieve N-α-alkylation at the α-C(sp³)-H site of N-aryl glycine derivatives. This method offers a novel approach for the synthesis of unnatural amino acids bearing diverse functional groups. The reaction proceeds under mild conditions and exhibits broad substrate scope, facilitating the preparation of a series of N-aryl glycine derivatives containing cyanoalkyl groups.

建立了光氧化催化的三组分反应，在该反应中，光催化剂介导的连续还原和氧化过程产生了两种不同的氮中心自由基。这种转化包括C-C键的裂解和α-氨基烷基自由基的生成作为平行的关键步骤，使烯烃二官能化在N-芳基甘氨酸衍生物的α- c (sp3)-H位点实现N-α-烷基化。该方法为合成具有不同官能团的非天然氨基酸提供了新的途径。该反应在温和的条件下进行，具有广泛的底物范围，有利于制备一系列含有氰烷基的n -芳基甘氨酸衍生物。

引用次数: 0

Photocatalytic in-situ reductive fragmentation and coupling of lignin β-O-4 linkages to pinacols 木质素β-O-4键与蒎醇的光催化原位还原断裂及偶联

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-21 DOI: 10.1016/j.jcat.2026.116714

Jingjing Yang , Ting Li , Chengyan Zou , Jinlan Cheng , Kaiyi Su , Bo Jiang , Hao Li , Zhengwei Li , Chaofeng Zhang

Compared with the aromatic monomer preparation, the lignin catalytic transformation to dimers with higher added value has received extensive attention recently. Different from the stepwise tandem synthesis strategies for dimer preparation, which involve the first lignin depolymerization to monomers and following monomer coupling to dimers, we here achieved the in-situ photocatalytic reductive fragmentation-coupling of the pre-oxidized lignin β-O-4 linkages to pinacols. The optimized TiO₂-R(1 1 0) (rutile) could efficiently achieve the transformation of 2-phenoxy-1-phenylethanone with i-PrOH as the hydrogen donor under UV LED irradiation, providing an 83.0% yield of 2,3-diphenylbutane-2,3-diol and a 78% yield of phenol in 15 h. Mechanism studies indicated that the activated TiO₂-R with critical surface Ti³⁺ species under UV LED irradiation mediated the first photocatalytic cleavage of the C_β–OAr bond of 2-phenoxy-1-phenylethanone to phenol and acetophenone. The generated acetophenone further underwent semi-reduction and carbon radical coupling to provide the pinacol, dominated by the UV LED irradiation and improved by the TiO₂-R(1 1 0) surface. The revelation of the catalytic mechanism can provide ideas for the subsequent direct conversion of lignin to high-value dimer products.

与芳香单体制备相比，木质素催化转化为高附加值的二聚体近年来受到了广泛的关注。不同于二聚体制备的逐步串联合成策略，即首先木质素解聚成单体，然后单体偶联成二聚体，我们在这里实现了预氧化木质素β-O-4键与蒎醇的原位光催化还原断裂偶联。优化TiO2-R(1 1 0)(金红石)可以有效地实现的变换与i-PrOH 2-phenoxy-1-phenylethanone氢供体在紫外线照射,提供一个83.0%的收益率,3-diphenylbutane-2 3-diol和苯酚的78%的收益率15 h。机制研究表明,激活与临界表面Ti3 +物种TiO2-R紫外LED照射下Cβ介导的第一光催化裂桨债券2-phenoxy-1-phenylethanone苯酚和苯乙酮。生成的苯乙酮进一步进行半还原和碳自由基偶联，以紫外LED照射为主，TiO2-R（11 10）表面对其进行修饰，得到苯乙酮。该催化机理的揭示为后续木质素直接转化为高价值二聚体产品提供了思路。

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引用次数: 0

Photocatalytic H2 production from HCOOH over Pd/TiO2: Pd2+/Pd0 self-cycle and adsorption-induced electron transfer mechanism HCOOH在Pd/TiO2上光催化制氢：Pd2+/Pd0自循环及吸附诱导的电子转移机理

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-12 DOI: 10.1016/j.jcat.2026.116697

Hong Wang , Yan Wang , Yong Jia , Lina Guo , Gang Cheng , Zhongming Wang , Kai Yang , Wenxin Dai

Research on the photocatalytic production of H₂ from HCOOH decomposition provides scientific guidance for hydrogen energy development. In this study, a Pd-doped oxygen-deficient TiO₂ catalyst featuring mixed-valence PdO_x atomic cluster nests, oxygen vacancies (Vo), and hydroxyl groups was synthesized. Activity tests revealed that 0.4 Pd-def-TiO₂ sample performed best under visible light, producing H₂ at a rate of 3180.66 μmol·g⁻¹·h⁻¹, a 124-fold enhancement over def-TiO₂. Combined characterization and theoretical calculation results showed that Pd-def-TiO₂ formed a “step-like” energy band structure, and the separation and transfer of photogenerated carriers have been optimized in conjunction with Vo and surface hydroxyl groups. Further, HCOOH adsorption was followed by the formation of a bidentate HCOO_BX species, in which one oxygen atom of the adsorbate was hydrogen bonded with a surface hydroxyl group, while the other end was adsorbed onto a Pd⁰ site. This process involved simultaneous electron loss and gain, resulting in a distinctive “valley-shaped” gas-sensing response, thus promoting directional activation of HCOOH, facilitating complete redox reactions. Moreover, photoreduction and Vo (near Pd sites) promoted electron delocalization in mixed-valent Pd²⁺/Pd⁰ species, enabling self-cycling of these active sites, leading to enhanced efficiency and stability during photocatalytic hydrogen evolution from HCOOH. This study contributes to the design of highly efficient and stable catalysts, and advances the understanding of the underlying reaction mechanisms.

HCOOH分解光催化制氢研究为氢能开发提供了科学指导。在本研究中，合成了一种具有混合价PdOx原子簇巢、氧空位（Vo）和羟基的掺杂pd的缺氧TiO2催化剂。活性测试表明，0.4 Pd-def-TiO2样品在可见光下的产氢速率为3180.66 μmol·g−1·h−1，比def-TiO2提高了124倍。结合表征和理论计算结果表明，Pd-def-TiO2形成了“阶梯状”能带结构，并结合Vo和表面羟基优化了光生载流子的分离和转移。此外，HCOOH吸附后形成双齿状HCOOBX，其中吸附物的一个氧原子与表面羟基形成氢键，而另一端被吸附在Pd0位点上。该过程涉及电子的同时损失和获得，导致独特的“谷形”气敏响应，从而促进HCOOH的定向活化，促进完整的氧化还原反应。此外，光还原和Vo（靠近Pd位点）促进了混合价Pd2+/Pd0的电子离域，使这些活性位点能够自循环，从而提高了HCOOH光催化析氢过程的效率和稳定性。该研究有助于设计高效、稳定的催化剂，并促进对潜在反应机理的理解。

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引用次数: 0

Bio-derived quantum dot based luminescent solar concentrator for photocatalytic conversion of fructose to 5-hydroxymethylfurfural via iron(II) complex catalysis 利用铁（II）配合物催化将果糖转化为5-羟甲基糠醛的生物衍生量子点发光太阳能聚光器

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-12 DOI: 10.1016/j.jcat.2026.116701

Mohammad Bashiri, Mona Hosseini-Sarvari

In the present study, a novel benzimidazole ligand was synthesized and used as a precursor for the preparation of iron(II) complex. Following the synthesis, a comprehensive array of experimental investigations was undertaken to explore the structural, photo-electronic, and electrochemical characteristics of the iron(II) complex. The complex was subsequently utilized as an efficient photocatalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from fructose. In this catalytic process, a luminescent solar concentrator (LSC) system was employed, further augmented by plant-derived quantum dots. This innovative optical system significantly enhanced the overall efficiency of the photocatalytic reaction. We selected a colorless transparent panel for the LSC device because the emission from the quantum dots falls within the blue region, which overlaps with the absorption spectrum of our complex and can promote the progress of the reaction. The yield of 5-hydroxymethylfurfural from fructose in this continuous flow system under solar irradiation was 91%, whereas in the batch system, a yield of only 70% was achieved under blue light irradiation. Furthermore, this work contributes novel insights into the potential of iron(II) complex-based photocatalysts for driving intricate chemical transformations under environmentally benign and sustainable conditions.

本研究合成了一种新型苯并咪唑配体，并将其作为制备铁（II）配合物的前驱体。在合成之后，进行了一系列全面的实验研究，以探索铁（II）配合物的结构、光电和电化学特性。该配合物随后被用作果糖选择性合成5-羟甲基糠醛（HMF）的有效光催化剂。在该催化过程中，采用了发光太阳能聚光器（LSC）系统，并通过植物衍生的量子点进一步增强。这种创新的光学系统显著提高了光催化反应的整体效率。我们选择了一个无色透明的面板作为LSC器件，因为量子点的发射落在蓝色区域，这与我们的配合物的吸收光谱重叠，可以促进反应的进行。该连续流系统在太阳照射下从果糖中提取5-羟甲基糠醛的收率为91%，而在批处理系统中，蓝光照射下的收率仅为70%。此外，这项工作为铁（II）配合物基光催化剂在环境友好和可持续条件下驱动复杂化学转化的潜力提供了新的见解。

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引用次数: 0

Synergistic effect of Cu+-Cu0 sites and oxygen vacancies at MOF-derived Cu-ZrO2 interface for the reverse water–gas shift reaction mof衍生Cu- zro2界面上Cu+-Cu0位点和氧空位的协同效应对逆向水气转移反应的影响

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-07 DOI: 10.1016/j.jcat.2026.116679

Huilin Zhou , Yahui Yang , Riying Zeng, Zhenzhen Huang, Qihan Huang, Yidan Li, Lihua Wang

The development of efficient and stable catalysts for the reverse water–gas shift (RWGS) reaction is crucial for mitigating CO₂ emissions. Although cost-effective, conventional copper-based catalysts suffer from valence fluctuations (between Cu⁺ and Cu⁰) and particle sintering. This study developed a Cu/ZrO₂ catalyst via a metal–organic framework (MOF) derivation strategy to enhance the interaction at Cu-ZrO₂ interface and the catalyst stability. Using a bimetallic MOF-818 as a precursor, the Cu/ZrO₂-MOF catalyst was prepared through pyrolysis/reduction. The catalyst exhibited abundant oxygen vacancies (19.1%) and an optimized Cu⁺/Cu⁰ ratio (1.12). Under RWGS conditions, CO₂ conversion reached 39.5% with complete CO selectivity at 450 ℃, surpassing the performance of conventional catalysts. Notably, it showed no significant deactivation over 224 h, including a period under high gas hourly space velocity. Post-reaction characterization confirmed the stability of active sites, which is attributed to the metal-support interaction. Mechanistic studies revealed a synergistic effect at the interface, whereby CO₂ is activated by Cu⁺ sites and oxygen vacancies, while H₂ is dissociated on Cu⁰ sites, which elucidates the synergistic mechanism of interfacial active sites and thus provides a general design strategy for developing sinter-resistant and high-performance Cu-based catalysts.

开发高效、稳定的水气反向变换（RWGS）催化剂对减少二氧化碳排放至关重要。尽管具有成本效益，但传统的铜基催化剂存在价态波动（在Cu+和Cu0之间）和颗粒烧结问题。本研究通过金属-有机骨架（MOF）衍生策略开发了Cu/ZrO2催化剂，以增强Cu-ZrO2界面的相互作用和催化剂的稳定性。以双金属MOF-818为前驱体，通过热解/还原法制备Cu/ZrO2-MOF催化剂。催化剂具有丰富的氧空位（19.1%）和优化的Cu+/Cu0比（1.12）。在RWGS条件下，450℃下CO2转化率达到39.5%，CO选择性完全，超过了常规催化剂的性能。值得注意的是，在224 h内，包括在高气体每小时空间速度下的一段时间内，它没有显示出明显的失活。反应后表征证实了活性位点的稳定性，这归因于金属-载体相互作用。机理研究揭示了界面上的协同效应，即CO2被Cu+位点和氧空位激活，而H2在Cu0位点解离，这阐明了界面活性位点的协同机制，从而为开发抗烧结和高性能的Cu基催化剂提供了总体设计策略。

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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 : 2026-03-01 Epub 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。

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引用次数: 0

The impact of active site character on the selectivity of aldehyde-ketone cross-aldol condensation reactions 活性位点特征对醛酮交叉醛缩反应选择性的影响

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-06 DOI: 10.1016/j.jcat.2026.116687

Brandon Elliott Oliphant, Zachary W. Meduna, J.Will Medlin

Mixed-aldol condensation of acetaldehyde and acetone was investigated over metal oxide and aluminosilicate catalysts to understand how changing the type of active site affects the selectivity of aldehyde-ketone cross-aldol condensation reactions. On TiO₂ and MgO, where basic sites play a central role, high selectivity toward acetaldehyde self-condensation was observed. In contrast, reactions on the aluminosilicates, catalyzed by acid sites, had high selectivity toward the cross-condensation reaction. Temperature programmed desorption (TPD) studies showed that TiO₂ binds acetaldehyde and its coupling products strongly, whereas acetone is adsorbed weakly enough to mostly undergo desorption without reaction. Similar studies on amorphous silica-alumina (ASA) showed the existence of both strongly bound acetaldehyde and strongly bound acetone, evidenced by the desorption of acetaldehyde and acetone coupling products. The discrepancy in reactant binding between surfaces is also supported by reaction order studies, which showed that on TiO₂ acetone does not displace acetaldehyde from the catalyst surface, whereas on the aluminosilicate catalysts acetone readily displaces acetaldehyde. Kinetic isotope effect experiments showed that although selectivity is different across the two types of catalysts, C–H bond activation to form the nucleophilic enolate is likely kinetically relevant on both materials. High selectivity to cross-condensation was observed on HZSM-5 with a variety of SiO₂:Al₂O₃ ratios, with kinetic results indicating a tradeoff between the number and strength of the active sites.

研究了乙醛和丙酮在金属氧化物和铝硅酸盐催化剂上的混合醛缩反应，以了解改变活性位点类型对醛酮交叉醛缩反应选择性的影响。在碱性位点起中心作用的TiO2和MgO上，观察到乙醛自缩合的高选择性。相比之下，酸位催化的铝硅酸盐上的反应对交叉缩合反应有很高的选择性。温度程序解吸（TPD）研究表明，TiO2与乙醛及其偶联产物结合较强，而丙酮的吸附较弱，大部分都是在不发生反应的情况下进行解吸。对无定形二氧化硅-氧化铝（ASA）的类似研究表明，存在强结合的乙醛和强结合的丙酮，乙醛和丙酮偶联产物的脱附证明了这一点。反应顺序的研究也支持了表面之间反应物结合的差异，表明在TiO2上丙酮不会从催化剂表面取代乙醛，而在铝硅酸盐催化剂上丙酮很容易取代乙醛。动力学同位素效应实验表明，尽管两种催化剂的选择性不同，但C-H键活化形成亲核烯酸酯可能在两种材料上具有动力学相关性。在不同SiO2:Al2O3配比下，HZSM-5具有较高的交叉缩聚选择性，动力学结果表明活性位点的数量和强度之间存在权衡。

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引用次数: 0

Cavity-confined Cu2O nanoreactors for efficient CO2 electroreduction to ethylene 腔限Cu2O纳米反应器用于高效CO2电还原乙烯

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-20 DOI: 10.1016/j.jcat.2026.116710

Xiao-Rong Wen , Shan-Shan Chen , Wen-Jun Xie , Hong-Ru Li , Liang-Nian He

Electrocatalytic carbon dioxide reduction (eCO₂R) to ethylene (C₂H₄) offers a promising pathway toward carbon–neutral cycles and sustainable chemical synthesis. In eCO₂R to C₂H₄, copper-based electrocatalysts, particularly Cu₂O, have been widely used. Nevertheless, product selectivity to C₂H₄ is still quite limited due to the insufficient enrichment of key intermediates and slow C–C coupling kinetics. Herein, the double-shelled hollow mesoporous Cu₂O was fabricated through the soft-templating method. And the cavity size and pore architecture of the resulting Cu₂O catalysts could be precisely tailored by adjusting the alkyl chain length of the surfactant templates alkyltrimethylammonium bromides. When applied to eCO₂R, the as-prepared Cu₂O material with tetradecyltrimethylammonium bromide (TTAB) as template exhibited a remarkable Faradaic efficiency of 43.3 ± 0.8% for C₂H₄ at an industrial-level current density of 549.8 mA cm⁻². Experimental and theoretical investigations reveal that its high activity and selectivity toward C₂H₄ stem from the suitable cavity configuration, which enriches key *CO intermediates and promotes their dimerization via a spatial confinement effect. This study provides valuable insights into the architectural design of efficient catalysts for CO₂-to-C₂H₄ conversion.

电催化二氧化碳还原（eCO2R）制乙烯（C2H4）为实现碳中性循环和可持续化学合成提供了一条有前途的途径。在eCO2R到C2H4中，铜基电催化剂，特别是Cu2O已被广泛使用。然而，由于关键中间体富集不足和C-C耦合动力学缓慢，产物对C2H4的选择性仍然很有限。本文采用软模板法制备了双壳中空介孔Cu2O。通过调整表面活性剂模板烷基三甲基溴化铵的烷基链长度，可以精确地调整Cu2O催化剂的空腔大小和孔结构。以十四烷基三甲基溴化铵（TTAB）为模板制备的Cu2O材料在工业级电流密度549.8 mA cm−2下，对C2H4的法拉第效率为43.3±0.8%。实验和理论研究表明，其对C2H4的高活性和选择性源于合适的腔体结构，它通过空间约束效应富集了关键的*CO中间体并促进了它们的二聚化。该研究为CO2-to-C2H4转化的高效催化剂的结构设计提供了有价值的见解。

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引用次数: 0