Molecular Catalysis最新文献_第2页

Engineering of FeS/NiS nanocomposites using biomass-derived carbon support to modulate spin polarization and catalytic properties 利用生物质衍生碳载体调节自旋极化和催化性能的FeS/NiS纳米复合材料工程

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-30 DOI: 10.1016/j.mcat.2026.115749

Prashant K. Bhartiya , Manish Srivastava , Debabrata Mishra

In this work, a chiral molecule-overlay FeS/NiS nanocatalyst supported by rice husk ash (RHA) derived graphene like carbon nanosheets (GLCN) is synthesized and electrochemically evaluated on a nickel foam (NiF) substrate for effective hydrogen evolution reactions (HER) and oxygen evolution reactions (OER). An abundant agricultural biowaste, RHA-derived GLCN makes it an eco-friendly alternative to expensive catalysts, which improves the stability and surface area of the catalyst by acting as a durable and porous support matrix. The assimilation of chiral coatings induces chiral-induced spin selectivity (CISS), which enhances both HER and OER performance. From electrochemical study, in alkaline conditions, the NiF-FeS/NiS/GLCN hybrid electrode with chiral molecules coating provides a remarkable overpotential of -109 mV for HER at -20 mAcm^-2 and 290 mV for OER at 20 mAcm^-2. The combined advantages of conductive FeS/NiS/GLCN active sites and spin-polarization effects provided by chiral coatings are responsible for this prominent enhancement in current density (

\sim 3 - f o l d

) both in OER & HER. The findings pave the way for the development of next-generation electrocatalysts that use sustainable materials and novel surface modifications to achieve effective energy conversion in water splitting applications.

在这项工作中，合成了一种手性分子覆盖的FeS/NiS纳米催化剂，该催化剂由稻壳灰（RHA）衍生的石墨烯类碳纳米片（GLCN）支撑，并在泡沫镍（NiF）衬底上进行了电化学评价，以进行有效的析氢反应（HER）和析氧反应（OER）。作为一种丰富的农业生物废弃物，rhaa衍生的GLCN使其成为昂贵催化剂的环保替代品，它作为一种耐用的多孔支撑基质，提高了催化剂的稳定性和表面积。手性涂层的同化作用诱导了手性诱导自旋选择性（CISS），提高了HER和OER性能。电化学研究表明，在碱性条件下，手性分子包覆的NiF-FeS/NiS/GLCN杂化电极在-20 mAcm-2下的过电位为-109 mV，在20 mAcm-2下的过电位为290 mV。导电FeS/NiS/GLCN活性位点的综合优势和手性涂层提供的自旋极化效应是OER和HER中电流密度显著增强（约3 -倍）的原因。这一发现为下一代电催化剂的开发铺平了道路，这些电催化剂使用可持续材料和新的表面修饰，在水分解应用中实现有效的能量转换。

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引用次数: 0

Unraveling the catalytic role of Fe2/Cu(111) diatomic sites in selective CO2 electroreduction to ethanol 揭示Fe2/Cu（111）双原子位在选择性CO2电还原制乙醇中的催化作用

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-30 DOI: 10.1016/j.mcat.2026.115750

Yilei Zhou, Zhiyuan Yang, Liyun Jiang, Qi Yu

In this work, density functional theory (DFT) is employed to explore the full reaction landscape of CO₂ reduction to C₂ species on Fe₂ diatomic sites supported by Cu(111) (Fe₂/Cu(111) DAC). Compared with the Fe single-atom catalyst (Fe₁/Cu(111) SAC), Fe₂/Cu(111) DAC shows stronger *CO₂ adsorption, promotes subsequent proton-coupled electron transfer (PCET) steps. Notably, the C-C coupling via *HCO-*HCOO is thermodynamically favorable (ΔG = 0.67 eV), and its kinetic feasibility is further evaluated by transition-state calculations. This pathway bypasses the HCOOH-forming route and suggests a preference toward CH₃CH₂OH. Electronic structure analysis reveals the underlying mechanism for CO₂ activation and C-C coupling.

本文采用密度泛函理论（DFT）研究了Cu（111）负载的Fe2双原子位（Fe2/Cu(111) DAC）上CO2还原为C2的完整反应过程。与Fe单原子催化剂（Fe1/Cu(111) SAC）相比，Fe2/Cu(111) DAC表现出更强的*CO2吸附，促进了后续质子耦合电子转移（PCET）步骤。值得注意的是，通过*HCO-*HCOO的C-C耦合在热力学上是有利的（ΔG = 0.67 eV），并且通过过渡态计算进一步评估了其动力学可行性。该途径绕过hcooh形成途径，并倾向于CH3CH2OH。电子结构分析揭示了CO2活化和碳-碳耦合的潜在机制。

引用次数: 0

Insights into the mechanism and stereoselectivity of chiral phosphoric acid‑catalyzed asymmetric Pictet–Spengler cyclization 手性磷酸催化不对称Pictet-Spengler环化的机理和立体选择性研究

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115754

Dong Xie , Hai-Rong Zhang , Xin-Ting He , Kai Wu , Hao Qiu , Zhe-Rui Zhang , Yu-Hao Qiao , Qinwei Yu , Pan-Pan Zhou

Density functional theory (DFT) calculations were employed to elucidate the catalytic mechanism and stereoselectivity control in the chiral phosphoric acid (CPA)-catalyzed asymmetric Pictet-Spengler cyclization. The computational study reveals that the CPA catalyst initially promotes the dehydration condensation between N-arylindole derivatives and m-cyanobenzaldehyde to form an iminium ion intermediate, which subsequently undergoes intramolecular electrophilic substitution with the indole ring to afford the final product. Four possible reaction pathways were systematically investigated and compared, enabling the identification of the most favorable pathway leading to the major product as well as a competing pathway yielding the minor enantiomer. The roles of noncovalent interactions, particularly hydrogen bonding interactions, were examined using QTAIM and IGMH analyses. Furthermore, EDA analysis was performed to unravel the origin of the high enantioselectivity. The calculated e.e. value of 99% is in excellent agreement with experimental observations. This work provides valuable mechanistic insights into the CPA-catalyzed asymmetric Pictet-Spengler cyclization and is expected to guide the future design of related stereoselective transformations.

采用密度泛函理论（DFT）分析了手性磷酸（CPA）催化的不对称Pictet-Spengler环化反应的催化机理和立体选择性控制。计算研究表明，CPA催化剂首先促进n -芳基吲哚衍生物与间氰苯甲醛之间的脱水缩合，形成胺离子中间体，随后与吲哚环发生分子内亲电取代，得到最终产物。系统地研究和比较了四种可能的反应途径，从而确定了产生主要产物的最有利途径以及产生次要对映体的竞争途径。非共价相互作用，特别是氢键相互作用的作用，使用QTAIM和IGMH分析进行了检验。此外，EDA分析揭示了高对映体选择性的起源。计算的e.e.值为99%，与实验结果非常吻合。这项工作为cpa催化的不对称Pictet-Spengler环化提供了有价值的机制见解，并有望指导未来相关立体选择转化的设计。

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引用次数: 0

Investigation on the effect of Na on Fe-Cu-Ce catalysts for ambient pressure hydrogenation of CO2 into olefins Na对Fe-Cu-Ce催化剂常压加氢制烯烃影响的研究

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115748

Mingyu Xie , Meixian Li , Weibin Liang, Xiyan Chen, Le Yang

Na is a performance enhancing and indispensable active species in Fe-based catalysts for CO₂ hydrogenation to olefin, as it promotes the formation of Fe₅C₂ and the adsorption of CO₂. The effect of Na is extensive far beyond this point and needs further investigation. Herein, the role of Na in the Fe-Cu-Ce catalysts is explored on NaFeCuCe and FeCuCe, which are prepared using NaOH and NH₃·H₂O, respectively. It is found that Fe₅C₂ abundance, Ce-O bond strength and Cu⁰/Cu⁺ compositions can be regulated via the doping of Na. The addition of Na significantly increases the abundance of Fe₅C₂, promoting both RWGS and FTS processes with higher conversion and olefin selectivity. Na also weakens Ce-O bond and thus facilitates adsorption and activation of CO₂. Cu exists in the form of Cu⁰ in NaFeCuCe while in the state of Cu⁺ in FeCuCe, and it is proposed that Cu⁰ performs more moderate in hydrogenation than Cu⁺, therefore inhibiting over hydrogenation. Notably, the differentiation of C in Fe-C and coke is distinguished using O₂-TPD-MS and CO₂-TPD-MS. Less coke is generated on NaFeCuCe, as carbon is more inclined to bond with Fe to form Fe₅C₂. Furthermore, Fe-C and Fe-O are distinguished using DRIFTS, with characteristic peaks at 875 and ∼860 cm^-1, respectively. The synergistic effect of Ce-O_v, Cu⁰ and Fe₅C₂ enables NaFeCuCe to achieve a CO₂ conversion of 16.8% and an olefin selectivity of 58.4% under ambient pressure at 300 °C. Compared with FeCuCe, the olefin selectivity is nearly 3.3 times higher.

Na是CO2加氢制烯烃的铁基催化剂中不可缺少的活性物质，它能促进Fe5C2的形成和对CO2的吸附。钠的作用远远超出了这一点，需要进一步研究。本文以NaOH和NH3·H2O分别制备的nafecce和fecce为催化剂，探讨了Na在Fe-Cu-Ce催化剂中的作用。通过Na的掺杂可以调节Fe5C2丰度、Ce-O键强度和Cu0/Cu+组成。Na的加入显著提高了Fe5C2的丰度，促进了RWGS和FTS工艺的转化率和烯烃选择性提高。Na也会削弱Ce-O键，从而促进CO2的吸附和活化。Cu在NaFeCuCe中以Cu0的形态存在，而在fececuce中以Cu+的形态存在，提出Cu0的加氢表现比Cu+更为温和，从而抑制过加氢。值得注意的是，用O2-TPD-MS和CO2-TPD-MS区分了Fe-C和焦炭中C的分化。在nafecce上产生的焦炭较少，因为碳更倾向于与铁结合形成Fe5C2。此外，Fe-C和Fe-O使用DRIFTS区分，特征峰分别在875和~ 860 cm-1。Ce-Ov、Cu0和Fe5C2的协同作用使NaFeCuCe在300℃环境压力下的CO2转化率为16.8%，烯烃选择性为58.4%。与fecce相比，烯烃选择性提高了近3.3倍。

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引用次数: 0

Activity and selectivity in VOC oxidation over commercial EnviCat® systems: Pelleted vs. grained catalysts 活性和选择性在VOC氧化上的商业EnviCat®系统：颗粒与颗粒催化剂

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115761

Květuše Jirátová, Jana Balabánová, Martin Koštejn, Pavel Topka

This study examines how catalyst morphology governs the activity and selectivity of volatile organic compound (VOC) oxidation over three commercial EnviCat® catalysts. Ethanol, acetone, and toluene were used as representative VOCs to evaluate the performance of pelletized catalysts relative to their grained counterparts. Catalyst shape strongly influenced conversion, by-product formation, and apparent activation temperatures. Grained Cu–Mn catalyst achieved 90 % ethanol-to-CO₂ conversion at 221 °C, whereas the pelletized form required 425 °C, illustrating substantial internal diffusion limitations. Pelletized catalysts suppressed acetaldehyde formation during ethanol oxidation but promoted undesired benzene formation during toluene oxidation, particularly over Pt-Pd catalysts. T₅₀ values for pelletized catalysts were up to 60 °C higher for ethanol and 45–49 °C higher for acetone, whereas negligible differences were observed for toluene oxidation on Pt-Pd due to hotspot formation. These results demonstrate that internal mass- and heat-transfer effects critically shape both reaction rates and selectivity, altering pathways toward harmful by-products. The findings provide benchmark data for laboratory studies on grained catalysts and offer guidance for the rational design of structured catalytic systems for VOC abatement.

本研究考察了三种商用EnviCat®催化剂的催化剂形态如何影响挥发性有机化合物（VOC）氧化的活性和选择性。以乙醇、丙酮和甲苯为代表的挥发性有机化合物，相对于颗粒状催化剂，评估了颗粒状催化剂的性能。催化剂形状对转化率、副产物形成和表观活化温度有很大影响。颗粒状Cu-Mn催化剂在221°C下实现了90%的乙醇到二氧化碳的转化，而颗粒状催化剂需要425°C，这说明了内部扩散的局限性。颗粒化催化剂在乙醇氧化过程中抑制乙醛的形成，但在甲苯氧化过程中促进不需要的苯的形成，特别是在Pt-Pd催化剂上。对于乙醇和丙酮，颗粒催化剂的T50值分别高出60°C和45-49°C，而对于Pt-Pd上的甲苯氧化，由于热点的形成，差异可以忽略不计。这些结果表明，内部质量和传热效应对反应速率和选择性都有重要影响，改变了产生有害副产物的途径。这些发现为颗粒催化剂的实验室研究提供了基准数据，并为合理设计用于VOC减排的结构化催化体系提供了指导。

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引用次数: 0

Morphology-controlled magnetic Co3O4/carbon composite catalyst via fiber-templated microwave synthesis for efficient NaBH4 hydrolysis 纤维模板微波合成形态可控磁性Co3O4/碳复合催化剂高效水解NaBH4

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115758

Zi Jia Low , Siew Xian Chin , Dengwei Hu , Kean Long Lim , Chin Hua Chia

The rational design of biomass-derived catalysts for practical application is often compromised by the intrinsic chemical heterogeneity and morphological randomness of raw feedstocks, leading to poor reproducibility. To address this challenge, this work establishes a controllable synthesis strategy based on a rapid fiber-templated microwave approach, employing filter paper-derived fiber (FPDF) as a standardized, sacrificial template to assist in tuning the morphology of the Co₃O₄/carbon catalysts. Unlike raw biomass, FPDF provides a high-purity, structurally uniform scaffold that minimizes physical disturbances arising from irregular template structures and uncontrolled inorganic dopants (e.g., K, Mg, Ca, Si), thereby ensuring a consistent carbonaceous matrix. By synergistically combining this uniform template with structure directing agents (SDAs), systematic morphological evolution of the catalysts was achieved, yielding snowflake-, microplate- and hexagonal microprism-like architectures. Comprehensive characterization confirms that the resulting hierarchical microstructures possess interparticle voids that facilitate mass transfer. The synthesized catalyst achieves a high hydrogen generation rate (HGR) of 6333.9 mL min⁻¹·g⁻¹ at 328 K with an apparent activation energy (Ea) of 49.4 kJ·mol⁻¹. Beyond initial activity, morphology-dependent stability is observed, with the microplate architecture showing superior durability, retaining 76.0% of its activity after five consecutive cycles. Catalytic performance is governed by combined effects of morphology, surface area, surface chemistry and cobalt loading. Notably, NaBH₄ hydrolysis induces magnetic behavior in the composite, enabling facile magnetic recovery. Overall, this study demonstrates a sustainable, scalable and chemically consistent strategy for designing morphology-tunable, magnetically separable Co₃O₄/carbon catalysts derived from biomass-based carbon sources for efficient hydrogen generation via NaBH₄ hydrolysis.

实际应用的生物质衍生催化剂的合理设计往往受到原料固有的化学异质性和形态随机性的影响，导致再现性差。为了解决这一挑战，本研究建立了一种基于快速纤维模板微波方法的可控合成策略，采用滤纸衍生纤维（FPDF）作为标准化的牺牲模板来帮助调整Co3O4/碳催化剂的形态。与原料生物质不同，FPDF提供了高纯度、结构均匀的支架，最大限度地减少了由不规则模板结构和不受控制的无机掺杂物（如K、Mg、Ca、Si）引起的物理干扰，从而确保了一致的碳质基质。通过将该均匀模板与结构导向剂（SDAs）协同结合，实现了催化剂的系统形态演化，形成了雪花状、微板状和六边形微棱镜状结构。综合表征证实，所得的分层微观结构具有有利于传质的粒子间空隙。合成的催化剂在328 K下的产氢速率为6333.9 mL min - 1·g - 1，表观活化能（Ea）为49.4 kJ·mol - 1。除了初始活性外，还观察到形态依赖的稳定性，微孔板结构表现出优异的耐久性，在连续5个周期后仍保持76.0%的活性。催化性能受形貌、表面积、表面化学和钴负载的综合影响。值得注意的是，NaBH4水解诱导了复合材料的磁性行为，使磁恢复变得容易。总的来说，这项研究展示了一种可持续的、可扩展的和化学上一致的策略，用于设计形态可调的、磁性可分离的Co3O4/碳催化剂，这些催化剂来源于生物质碳源，通过NaBH4水解高效制氢。

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引用次数: 0

Hollow core-shell Co9S8@ZnIn2S4 S-scheme heterojunction for selective CO2-to-CO photoreduction 空心核壳Co9S8@ZnIn2S4选择性CO2-to-CO光还原的s型异质结

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115747

Yifan Wang , Diana Vanessa Cordero Rodríguez , Fengyu Tian , Jiayu Liang , Xuemin Yan

Photocatalytic CO₂ conversion is considered a promising approach to address energy and environmental challenges through the production of renewable fuels. The rational design of high-performance photocatalysts relies on precise band structure engineering and controlled nano-architectural design. This work presents a hollow core-shell Co₉S₈@ZnIn₂S₄ (CoS@ZIS) S-scheme heterojunction for highly selective photocatalytic CO₂ reduction to CO. The composite was synthesized by growing ultrathin ZnIn₂S₄ nanosheets on Co₉S₈ polyhedral cages derived from ZIF-67, forming a hierarchical architecture. This unique structure provides abundant active sites and enhances charge separation. Combined experimental analyses confirm the formation of an internal electric field at the heterointerface, which drives an S-scheme charge transfer pathway. This mechanism effectively separates electron-hole pairs while preserving strong redox capabilities. As a result, the optimized CoS@ZIS catalyst achieves a remarkable CO production rate of 5.81 μmol·g⁻¹·h⁻¹ under visible light irradiation, significantly outperforming its individual components.

光催化二氧化碳转化被认为是通过生产可再生燃料来解决能源和环境挑战的一种有前途的方法。高性能光催化剂的合理设计依赖于精确的能带结构工程和可控的纳米结构设计。本文提出了一种用于高选择性光催化CO2还原为CO的中空核壳Co9S8@ZnIn2S4 (CoS@ZIS) S-scheme异质结。该复合材料是通过在由ZIF-67衍生的Co9S8多面笼上生长超薄ZnIn2S4纳米片合成的，形成了层叠结构。这种独特的结构提供了丰富的活性位点，增强了电荷分离。结合实验分析证实在异质界面处形成内部电场，驱动S-scheme电荷转移途径。这种机制有效地分离了电子空穴对，同时保持了很强的氧化还原能力。结果表明，优化后的CoS@ZIS催化剂在可见光照射下CO的产率为5.81 μmol·g−1·h−1，明显优于其单个组分。

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引用次数: 0

CeO2 modification enhances carbon deposition resistance of Ni/MgAl2O4 in methane dry reforming CeO2改性提高了Ni/MgAl2O4在甲烷干重整中的抗积碳能力

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115740

Shuqin Gao , Yujie Niu , Peixu Wei , Yanan Li , Jinlei Wu , Lan Zheng , Le Wu , Yuqi Wang

Dry reforming of methane (DRM) is an effective method to achieve carbon emission reduction by directly converting CH₄ and CO₂, two of the world's most abundant greenhouse gases, into value-added products. However, conventional Ni-based catalysts are prone to metal sintering and carbon deposition, and the design of high-performance catalysts is proved to be critical for DRM. In this study, MgAl₂O₄ support and Ni/MgAl₂O₄-x%CeO₂ sample are prepared by sol-gel and ultrasound-assisted impregnation method, respectively. Compared with Ni/MgAl₂O₄, the Ni/MgAl₂O₄–10 % CeO₂ sample exhibits a 12.7 % higher oxygen vacancy concentration and twice as much surface basic sites. Meanwhile CeO₂ contributes abundant oxygen vacancies and basic sites, thereby enhancing the CO₂ decomposition capability. The resulting O* species participate in the carbon gasification reaction, leading to a reduced carbon deposition amount as expected. Notably, Ni/MgAl₂O₄–10 % CeO₂ manifests superior reducibility and eminent Ni dispersion. After 6 h activity test, the average Ni particle size increases by only 1.3 nm, indicating that the 10 % CeO₂ addition could enhance the sintering resistance for the as-prepared catalysts. As a result, the Ni/MgAl₂O₄-10 % CeO₂ sample delivers the best performance as desired, demonstrating only a 2.2 % drop of CO₂ conversion after 30 h DRM reaction.

甲烷干重整是将CH4和CO2这两种世界上最丰富的温室气体直接转化为增值产品，从而实现碳减排的一种有效方法。然而，传统的镍基催化剂容易发生金属烧结和碳沉积，高性能催化剂的设计对DRM至关重要。本研究采用溶胶-凝胶法制备MgAl2O4载体，超声辅助浸渍法制备Ni/MgAl2O4-x%CeO2样品。与Ni/MgAl₂O₄相比，Ni/MgAl₂O₄- 10% ceo2样品的氧空位浓度提高了12.7%，表面碱性位增加了两倍。同时，ce2提供了丰富的氧空位和碱性位点，从而提高了CO₂的分解能力。生成的O*物质参与了碳气化反应，使碳沉积量如预期的那样减少。值得注意的是，Ni/MgAl₂O₄- 10% CeO₂具有优异的还原性和优异的Ni分散性能。经过6 h的活性测试，Ni的平均粒径仅增加了1.3 nm，表明添加10%的CeO 2可以提高所制备催化剂的抗烧结性能。结果，Ni/MgAl₂O₄- 10% CeO₂样品提供了理想的最佳性能，在30小时的DRM反应后，CO₂转化率仅下降2.2%。

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引用次数: 0

Sustainable conversion of biogenic citronellal to cis-p-menthane-3,8-diol via tailored Cr-doped sulfonated biochar catalyst 通过定制的铬掺杂磺化生物炭催化剂可持续地将生物香茅醛转化为顺式对甲烷-3,8-二醇

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-29 DOI: 10.1016/j.mcat.2026.115735

Prashant Kumar , Priyabrat Mohapatra , Chandan Singh Chanotiya , Mohd Faizan Husain , Himmat Singh , Narayan Prasad Yadav , Suresh Kumar Bhargava , Selvakannan Periasamy , Ylias Sabri , Prasant Kumar Rout

p-Menthane-3,8-diol (PMD) is a bio-derived mosquito repellent valued for its low toxicity and environmental safety compared to synthetic alternatives such as DEET. Here, we report a sustainable catalytic pathway for the selective semi-synthesis of PMD from citronellal-rich essential oils using Cr-functionalized sulfonated biochar (Cr-SBC-HT) derived via hydrothermal carbonization. The tailored 5 %Cr-SBC-HT catalyst delivered 99 % conversion of citronellal and 96.7 % selectivity towards cis-PMD (cis/trans ratio 93:7) under mild conditions (60 °C, 85 min, 15 wt % catalyst). The catalyst exhibited robust structural integrity and reusability across ten cycles, underpinned by detailed physicochemical characterization (XRD, FT-IR, BET, TGA, SEM, HRTEM, XPS). Process optimization using response surface methodology (RSM)-box behnken design (BBD) further improved efficiency. The methodology demonstrated excellent green metrics, with a Process mass intensity (PMI) of 1.045, Turnover number (TON) of 386, Turnover frequency (TOF) of 272 h⁻¹, and an E-factor of 0.045. The enriched cis-PMD has displayed mosquito repellency for up to 6 h against Aedes species, confirming its practical application. This study highlighted the role of biomass-derived catalysts in enabling scalable, durable, and environmentally benign chemical manufacturing, bridging green materials development with bioactive product synthesis.

对甲基甲烷-3,8-二醇（PMD）是一种生物衍生的驱蚊剂，与避蚊胺等合成替代品相比，它具有低毒和环境安全的优点。在这里，我们报道了一种可持续的催化途径，利用水热碳化衍生的cr功能化磺化生物炭（Cr-SBC-HT），从富含香茅醛的精油中选择性半合成PMD。定制的5% Cr-SBC-HT催化剂在温和的条件下（60°C， 85分钟，15 wt %的催化剂），香茅醛的转化率为99%，顺式pmd的选择性为96.7%（顺反比93:7）。通过详细的物理化学表征（XRD, FT-IR， BET， TGA， SEM， HRTEM， XPS），该催化剂表现出坚固的结构完整性和可重复使用性。采用响应面法(RSM)-盒氏设计（BBD）的工艺优化进一步提高了效率。该方法证明了良好的绿色指标，过程质量强度（PMI）为1.045，周转数（TON）为386，周转频率（TOF）为272 h⁻¹，e因子为0.045。富集的顺式pmd对伊蚊的驱蚊效果长达6小时，证实了其实际应用价值。这项研究强调了生物质衍生催化剂在实现可扩展、耐用和环保的化学制造方面的作用，将绿色材料开发与生物活性产品合成联系起来。

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引用次数: 0

Valorization of shell waste-derived chitin into organonitrogen chemical 3-acetamido-5-acetylfuran with a new homogeneous tandem catalytic system 新型均相串联催化体系催化壳类废弃物甲壳素转化为有机硝基化合物3-乙酰氨基-5-乙酰呋喃

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-28 DOI: 10.1016/j.mcat.2026.115708

Changchun Wu , Yulong Chang , Xingxing Zhang, Xiangling Zhu, Qian Yang, Shuqian Xue, Antong Li, Hongjun Zang

The production of fine chemicals is increasingly shifting towards sustainability, emphasizingrenewable feedstocks and green processes. Among various bioresources, chitin has emerged as a promising renewable feedstock for the preparation of organonitrogen chemicals independent of the Haber-Bosch process. However, efficient conversion of chitin into the nitrogenous platform chemical 3-acetamido-5-acetylfuran (3A5AF) using heterogeneous catalytic system has been hindered by harsh reaction conditions, environmentally unfriendly processes, and lower catalytic efficiencies. Herein, we present a new chitin dissolution/homogeneous tandem catalysis strategy for the efficient one-step transformation of chitin to 3A5AF for the first time. As a result, an efficient, scalable, and homogeneous tandem catalytic system using the metal-based DES AlCl₃–2ChCl was established, achieving yields of 80.8% from monomer N-acetyl-d-glucosamine (NAG) and 33.4% from chitin, respectively. Notably, this homogeneous tandem catalytic system demonstrated scalability on a 2 g (9.0 mmol) scale of NAG, affording 3A5AF in 59.4% isolated yield. Furthermore, a shell biorefinery process for the direct production of 3A5AF from shrimp shell waste was successfully achieved. Our results reveal that the dissolution-homogeneous tandem catalysis effect is critical for enhancing product yields and minimizing side reactions. Moreover, the relationship between chitin structure and 3A5AF yield is thoroughly elaborated, demonstrating that both the solubility and degree of deacetylation of chitin determine the production of 3A5AF. This homogeneous tandem system holds practical application potential for the production of 3A5AF and provides new insights into shell biorefinery for the efficient synthesis of organonitrogen chemicals.

精细化学品的生产日益转向可持续性，强调可再生原料和绿色工艺。在各种生物资源中，甲壳素已成为一种有前途的可再生原料，可独立于Haber-Bosch工艺制备有机氮化学品。然而，利用多相催化体系将几丁质高效转化为含氮平台化学物质3-乙酰氨基-5-乙酰呋喃（3A5AF）一直受到反应条件苛刻、工艺环境不友好和催化效率低等问题的阻碍。本文首次提出了一种新的甲壳素溶解/均相串联催化策略，可将甲壳素一步高效转化为3A5AF。结果表明，采用金属基DES AlCl3-2ChCl建立了高效、可扩展、均相的串联催化体系，单体n -乙酰-d-氨基葡萄糖（NAG）的产率为80.8%，甲壳素的产率为33.4%。值得注意的是，该均相串联催化体系在2 g (9.0 mmol) NAG规模上具有可扩展性，3A5AF的分离产率为59.4%。此外，还成功地实现了虾壳废弃物直接生产3A5AF的壳生物炼制工艺。我们的研究结果表明，溶解-均相串联催化效应对提高产物收率和减少副反应至关重要。深入阐述了几丁质结构与3A5AF产率的关系，证明了几丁质的溶解度和去乙酰化程度都决定了3A5AF的产率。该均相串联体系具有生产3A5AF的实际应用潜力，并为壳生物精馏高效合成有机氮化学品提供了新的见解。

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