燃料化学学报最新文献_第2页

Progress in green methanol synthesis from municipal solid wastes 城市生活垃圾绿色甲醇合成研究进展

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60589-5

Ming LI , Dezhen CHEN , Kezhen QIAN , Yuyan HU

The mass generation of municipal solid waste (MSW) poses a serious challenge to the ecological environment and remains a critical problem worldwide. Methanol is an important raw material of modern industry which also serves as clean fuel to transportation, energy storage, etc. The production of methanol by using MSW as feedstock not only mitigates environmental challenges but also provides a renewable source, offering substantial environmental and economic benefits. This work focuses on the progress of the MSW-to-methanol processes. Firstly, the conversion routes of MSW-to-methanol including pyrolysis, gasification, anaerobic digestion and electrolysis are reviewed from the perspective of the technology maturity and economics. Among these routes, the methanol synthesis based on MSW gasification is the main pathway owing to the technological maturity and economic feasibility. Therefore, the second section focuses on the MSW gasification and optimization of syngas quality. Thirdly, the catalysts adopted in the methanol synthesis have been evaluated. Finally, the progress of the industrialization of MSW-to-methanol is reviewed. The prospects will be closely related to the one-step preparation of high-quality syngas, synergistic conversion of syngas with extra H₂ sources and the optimization of low-temperature catalysts for methanol synthesis.

城市生活垃圾的大量产生对生态环境造成了严重的挑战，在世界范围内仍然是一个严峻的问题。甲醇是现代工业的重要原料，也是交通运输、能源储存等领域的清洁燃料。利用城市生活垃圾作为原料生产甲醇不仅减轻了环境挑战，而且提供了可再生资源，提供了可观的环境和经济效益。本文重点介绍了固体垃圾制甲醇工艺的研究进展。首先，从技术成熟度和经济性的角度综述了生活垃圾制甲醇的几种转化途径，包括热解、气化、厌氧消化和电解。其中，基于生活垃圾气化的甲醇合成是技术成熟和经济可行的主要途径。因此，第二部分重点研究城市生活垃圾气化及合成气质量优化。第三，对甲醇合成中采用的催化剂进行了评价。最后，综述了城市生活垃圾制甲醇的工业化进展。高质量合成气的一步法制备、合成气与附加H2源的协同转化、甲醇合成低温催化剂的优化等是其发展前景。

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引用次数: 0

Effects of particle size of green mosaic coke on microstructure, electrical conductivity and oxidation behavior of the calcined coke 绿色马赛克焦的粒度对煅烧焦的微观结构、电导率和氧化行为的影响

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60586-X

Jiao HUANG, Yuzhu ZHANG, Yaming ZHU, Jiaxing YUE, Junxia CHENG, Xuefei ZHAO

As a key precursor material for carbon, the initial particle size of mosaic coke is a critical control parameter in industrial production process. This study systematically explains impact of initial particle size of mosaic coke on microcrystalline structure, conductivity, and oxidation behavior of the calcined coke. Different particle sizes of green mosaic coke (13−420 μm) were calcined at 1400°C and 1600°C. Using various characterization techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TG/DTG), the study explores effect of particle size on carbon microcrystalline structure, surface morphology, conductivity, and oxidation resistance of a calcined mosaic coke. The research shows that high-temperature calcination and particle size refinement work synergistically to promote the ordered transformation of carbon structure, effectively enhancing conductivity of the calcined coke. High-temperature treatment promotes formation of more oriented carbon layers inside the mosaic coke, especially with significant anisotropic features observed in samples with a particle size ≤ 45 μm. Oxidation kinetics indicate that the number of active sites on surface of the calcined coke, along with the degree of order in its microcrystalline structure, jointly control its oxidation process. This study provides an important theoretical basis for the particle size-structure-function synergistic regulation of performance-oriented coke materials.

马赛克焦作为碳的关键前驱体材料，其初始粒度是工业生产过程中一个重要的控制参数。本研究系统地解释了马赛克焦初始粒度对焦炭微晶结构、电导率和氧化行为的影响。在1400℃和1600℃下煅烧不同粒径（13 ~ 420 μm）的绿马赛克焦。利用扫描电镜（SEM）、x射线衍射（XRD）和热重分析（TG/DTG）等表征技术，研究了煅烧马赛克焦的粒度对碳微晶结构、表面形貌、电导率和抗氧化性的影响。研究表明，高温煅烧与粒度细化协同作用，促进了碳结构的有序转变，有效提高了煅烧焦炭的导电性。高温处理促进马赛克焦内部形成更多取向的碳层，特别是在粒径≤45 μm的样品中观察到明显的各向异性特征。氧化动力学表明，煅烧焦炭表面活性位点的数量及其微晶结构的有序程度共同控制着其氧化过程。该研究为性能取向焦炭材料的粒径-结构-功能协同调控提供了重要的理论依据。

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引用次数: 0

Recent advances in catalytic hydrogenation of furfural and its derivatives to value-added chemicals over non-noble metal catalysts 非贵金属催化剂催化糠醛及其衍生物加氢制备高附加值化学品的研究进展

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60553-6

Yueqing WANG , Weijie SHEN , Li DONG , Guoqing DING , Yulei ZHU

The increasingly severe environmental and energy challenges are driving the demand to produce chemicals and energy substances from renewable resources. Among industrially produced biomass-derived compounds, furfural is recognized as an important platform molecule. It can be converted into various value-added chemicals such as furan derivatives, diols and carboxylic acids via catalytic hydrogenation, hydrogenolysis, and oxidation. Selective activation of C=C, C=O and C−O bonds during the hydrogenation of furfural and its derivatives represents a primary pathway for furfural valorization. However, achieving selective scission of these bonds using non-noble metal catalysts under mild reaction conditions remains challenging. This review summarizes recent advances in using non-noble metal catalysts (Cu-, Ni-, and Co-based catalysts) for the catalytic hydrogenation of furfural and its derivatives to produce furfuryl alcohol, 2-methylfuran, 1,5-pentanediol, and 1,2-pentanediol. Some strategies such as fabricating bimetallic sites, metal-oxide interfaces, and metal-acid sites enable selective activation of specific chemical bonds. Nevertheless, the understanding of the dynamic catalytic processes at active centers under real reaction conditions remains insufficient. Advanced operando characterization techniques can provide deep insights into the dynamic evolution of active sites during reactions, helping to clarify the deactivation mechanisms of non-noble metal catalysts. The non-noble metal catalysts show great potential for the large-scale, high-value conversion of furfural and its derivatives, making this field a key focus for future biomass catalytic processes.

日益严峻的环境和能源挑战推动了对利用可再生资源生产化学品和能源物质的需求。在工业生产的生物质衍生化合物中，糠醛是公认的重要平台分子。它可以通过催化加氢、氢解和氧化转化为各种增值化学品，如呋喃衍生物、二醇和羧酸。在糠醛及其衍生物加氢过程中，C=C、C=O和C−O键的选择性活化是糠醛增值的主要途径。然而，在温和的反应条件下使用非贵金属催化剂实现这些键的选择性断裂仍然具有挑战性。本文综述了近年来利用非贵金属催化剂（铜基、镍基和钴基催化剂）催化糠醛及其衍生物加氢制备糠醇、2-甲基呋喃、1,5-戊二醇和1,2-戊二醇的研究进展。一些策略，如制造双金属位点、金属-氧化物界面和金属-酸位点，可以选择性地激活特定的化学键。然而，对实际反应条件下活性中心的动态催化过程的了解仍然不足。先进的operando表征技术可以深入了解反应过程中活性位点的动态演变，有助于阐明非贵金属催化剂的失活机制。非贵金属催化剂在糠醛及其衍生物的大规模、高价值转化方面显示出巨大的潜力，使该领域成为未来生物质催化过程的重点。

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引用次数: 0

Study on the performance and mechanism of Ni/CaO-CeZrO2 coupling CO2 capture and dry reforming of methane Ni/CaO-CeZrO2耦合CO2捕集与甲烷干重整的性能与机理研究

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60572-X

Yuhao CHEN, Xing ZHU, Min LIN, Hengyu WEI, Di GAO

The coupled technology of calcium looping and dry reforming of methane (CaL@DRM) shows great promise in the fields of CO₂ capture and conversion, as well as the resource-utilization of methane. Nevertheless, traditional calcium-based adsorbents are prone to sintering and coking at high temperature, which severely restricts their performance. In this study, a series of Ni/CaO-CeZrO₂ bifunctional catalysts were prepared via a combination of co-precipitation and impregnation methods, based on the traditional Ni/CaO, and applied to CaL@DRM. The catalysts were characterized by XRD, SEM, EDS, XPS, TG, Raman, etc., and their CaL@DRM performance was investigated. Experimental results demonstrate that, at 650 ℃, the Ni/10CaO-CeZrO₂ catalyst achieves a CO₂ capture rate of 2.00 mmol/g, a CH₄ conversion rate as high as 95%, and a CO selectivity of 79%. Its performance significantly outperforms most reported bifunctional materials and traditional dry reforming of methane catalysts. Moreover, after 50 cycles of testing, no significant decline in catalytic activity is observed. CaO provides basic active sites and adsorption capacity for CO₂ capture. The introduction of CeZrO₂ significantly increases the lattice oxygen content of the material, enhances the dispersion of Ni, promotes CO₂ capture and dry reforming of CH₄, and effectively suppresses sintering and coking, thus greatly improving the cyclic stability of CaL@DRM. This study provides a theoretical basis for a deeper understanding of the coupling process of CO₂ capture and dry reforming of methane, and offers guidance for the design and development of high-performance multifunctional materials.

钙环法与甲烷干重整耦合技术（CaL@DRM）在二氧化碳捕集与转化、甲烷资源化利用等领域具有广阔的应用前景。然而，传统的钙基吸附剂在高温下容易烧结和结焦，严重制约了其性能。本研究在传统Ni/CaO的基础上，通过共沉淀法和浸渍法制备了一系列Ni/CaO- cezro2双功能催化剂，并应用于CaL@DRM。采用XRD、SEM、EDS、XPS、TG、Raman等手段对催化剂进行了表征，并对催化剂的CaL@DRM性能进行了研究。实验结果表明，在650℃下，Ni/10CaO-CeZrO2催化剂的CO2捕集率为2.00 mmol/g， CH4转化率高达95%，CO选择性为79%。其性能明显优于大多数报道的双功能材料和传统的甲烷干重整催化剂。此外，经过50次循环测试，没有观察到催化活性明显下降。CaO为CO2捕获提供了基本的活性位点和吸附能力。CeZrO2的引入显著提高了材料的晶格氧含量，增强了Ni的分散性，促进了CO2的捕获和CH4的干重整，有效地抑制了烧结和结焦，从而大大提高了CaL@DRM的循环稳定性。本研究为深入了解CO2捕集与甲烷干重整的耦合过程提供了理论基础，并为高性能多功能材料的设计与开发提供了指导。

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引用次数: 0

La-modified Cu-Al spinel catalysts for hydrogen production via methanol steam reforming la改性Cu-Al尖晶石甲醇蒸汽重整制氢催化剂

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60574-3

Yongzhu CHEN , Daosheng LIU , Yongfu ZHAO , Caishun ZHANG , Honghao WANG , Yajie LIU , Jiao HAN , Lei ZHANG , Zhixian GAO

A series of surface-modified Cu_1−xLa_xAl_2.5 spinel catalysts with La were prepared by using the impregnation method and used in the methanol steam reforming (MSR) for hydrogen production. The interaction between La and the spinel catalyst, along with its effect on the sustained release of copper species, was investigated with the help of XRD, N₂ sorption, H₂-TPR, and XPS characterization techniques. The results indicate that La modification not only alters the microenvironment of Cu species and enhances the oxygen adsorption, but also promotes the formation of Al–O–La bonds, resulting in a stable interfacial structure. The Cu_1−xLa_xAl_2.5 spinel catalysts can be applied to the MSR reaction without pre-reduction treatment. Under 260 ℃, a water-to-alcohol molar ratio of 2, and a methanol mass space velocity of 2.0 h⁻¹, the optimal catalyst Cu_0.9La_0.1Al_2.5 maintains a stable methanol conversion of approximately 94% during a continuous reaction lasting for 136 h. In comparison with the unmodified catalyst, the catalytic activity of Cu_0.9La_0.1Al_2.5 is 5% higher, in addition to a decreased selectivity to CO by 20%. Further studies reveal that the Cu_0.9La_0.1Al_2.5 catalyst has the lowest Cu sustained release rate and the minimal Cu grain size after prolonged reaction, indicating that La modification plays a crucial role in determining the sustained release rate and the fate of the Cu species.

采用浸渍法制备了一系列La表面修饰Cu1−xLaxAl2.5尖晶石催化剂，并将其用于甲醇蒸汽重整制氢。利用XRD、N2吸附、H2-TPR和XPS表征技术研究了La与尖晶石催化剂的相互作用及其对铜缓释的影响。结果表明，La修饰不仅改变了Cu的微环境，增强了氧吸附，而且促进了Al-O-La键的形成，形成了稳定的界面结构。Cu1−xLaxAl2.5尖晶石催化剂无需预还原处理即可应用于MSR反应。在260℃、水醇摩尔比为2、甲醇质量空速为2.0 h−1的条件下，最优催化剂Cu0.9La0.1Al2.5在连续反应136 h时，甲醇转化率稳定在94%左右。与未改性催化剂相比，Cu0.9La0.1Al2.5的催化活性提高了5%，但对CO的选择性降低了20%。进一步研究发现，Cu0.9La0.1Al2.5催化剂的Cu缓释率最低，反应时间延长后Cu晶粒尺寸最小，表明La修饰对Cu的缓释率和Cu的命运起着至关重要的作用。

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引用次数: 0

Tailoring of Pt particle density on the surface of dealuminated ZSM-5 and its hexane cracking performance 脱铝ZSM-5表面Pt颗粒密度的变化及其己烷裂解性能

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60571-8

Dengrong XUE , Ruilin LIU , Zhongjie FENG , Yong QIN , Bin ZHANG

In this study, by loading platinum (Pt) at varying mass percentages onto acid-treating ZSM-5 zeolite with different silica-to-alumina ratio (SAR) and distinct surface acid sites via the metal-organic solid-phase synthesis method, the influence of metal-acid site ratios on the catalytic cracking of n-hexane to propane was investigated. Results demonstrated that acid treatment significantly increased the SAR of the zeolite (from 27 to 100), optimized the distribution of surface acid sites, while preserving the MFI topology. Post-Pt loading and reduction, the catalyst exhibited highly dispersed Pt nanoparticles(3.3–4.1 nm) without forming crystalline aggregates. Catalytic performance tests revealed that acid treatment enhanced the n-hexane conversion rate from 66% to 88% and propane selectivity from 50% to 57%. Pt loading exhibited a pronounced influence on performance: the medium-loaded catalyst (0.3%) achieved the highest propane selectivity (57%) and stability due to optimal metal-acid synergy. XPS and CO-DRIFTS analyses indicated that Pt loading reduced the electron density of oxygen species, thereby strengthening metal-acid interactions. This work provides a catalyst design strategy for the efficient and directional conversion of n-hexane.

本研究采用金属-有机固相合成方法，将不同质量百分比的铂（Pt）加载到具有不同硅铝比（SAR）和不同表面酸位的酸处理ZSM-5沸石上，研究了金属-酸位比对正己烷催化裂化制丙烷的影响。结果表明，酸处理显著提高了沸石的SAR（从27增加到100），优化了表面酸位的分布，同时保持了MFI拓扑结构。Pt负载还原后，催化剂表现出高度分散的Pt纳米颗粒（3.3-4.1 nm），未形成结晶聚集体。催化性能测试表明，酸处理将正己烷转化率从66%提高到88%，丙烷选择性从50%提高到57%。Pt负载对性能有显著的影响：中等负载的催化剂（0.3%）由于最佳的金属-酸协同作用，获得了最高的丙烷选择性（57%）和稳定性。XPS和CO-DRIFTS分析表明，Pt负载降低了氧的电子密度，从而加强了金属-酸的相互作用。本研究为正己烷的高效定向转化提供了一种催化剂设计策略。

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引用次数: 0

Photocatalytic C−C coupling of acetonitrile into succinonitrile over hydrophobic TiO2 in a flow reactor 在流动反应器中疏水TiO2上光催化C−C偶联乙腈成琥珀腈

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60580-9

Kun GONG , Min HUANG , Ruitao LI , Yuanyuan DAI , Qiang NIU , Tiejun LIN , Liangshu ZHONG

A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO₂ photocatalyst with enhanced catalytic activity was developed. In addition, the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature. The space time yield of succinonitrile reached 55.59 μmol/(g·h) over hydrophobic TiO₂ catalyst, which was much higher than that of pristine TiO₂ (4.23 μmol/(g·h)). Mechanistic studies revealed that the hydrophobic modification of TiO₂ promoted the separation and transfer of photogenerated carriers, as well as suppressed their recombination. Hydrophobic TiO₂ also enhanced the adsorption of −CH₃ of acetonitrile, thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.

在疏水TiO2光催化剂上，建立了乙腈自由基C−C偶联成琥珀腈的反应。此外，流动反应器的使用进一步提高了室温合成丁二腈的光子利用效率。在疏水TiO2催化剂上，丁二腈的时空产率达到55.59 μmol/(g·h)，远高于原始TiO2的4.23 μmol/（g·h）。机理研究表明，TiO2的疏水修饰促进了光生载体的分离和转移，同时抑制了它们的重组。疏水性TiO2还增强了乙腈对−CH3的吸附，从而促进了C−H键的活化和光载体的利用效率。

引用次数: 0

Preparation and performance of spatially confined catalysts Ni@CNTs for CO2 hydrogenation to methane CO2加氢制甲烷催化剂Ni@CNTs的制备与性能研究

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60585-8

Shibo ZHANG, Haiming XING, Xinying HE, Yanqin TAN, Hui LUO, Feng DU, Wenan DENG, Chuan LI

Multi-walled carbon nanotubes (CNTs) were treated by acid oxidation-ultrasonication. Nickel-based catalysts with spatial confinement were prepared using both pristine and treated CNTs as the encapsulating layer. The effects of the treatment on CNT length, structural properties, and the size of the incorporated nickel particles were investigated by scanning electron microscopy (SEM), Raman spectroscopy and nitrogen physisorption (BET). The catalytic performance of the catalyst for the CO₂ methanation reaction was evaluated. The results show that acid oxidation-ultrasonic treatment can significantly shorten the length of the CNTs. This length reduction facilitates a higher incorporation efficiency of nickel particles. Compared with the untreated nanoscale CNTs, the average length of CNTs treated with mixed acid (concentrated sulfuric acid and concentrated nitric acid in the ratio of 3:1 by volume) for 45 min and ultrasonic for 2 h is reduced to about 100 nm and the nickel-metal filling efficiency increase from 34.65% to 93.84%. In addition to shortening CNT length, the acid oxidation-ultrasonication treatment can introduce structural defects in the CNT walls both and increase both the pore volume and specific surface area of CNTs, which can promote the efficient encapsulation of nickel metals within CNTs. The confinement effect of CNTs successfully reduces the average particle size of nickel-metal from 14.92 nm to 7.14 nm and improves metal dispersion. Consequently, the confined catalyst exhibits enhanced activity in CO₂ methanation, achieving a CO₂ conversion of 79.52% and a methane selectivity of 98.98%.

采用酸氧化-超声法处理多壁碳纳米管。采用原始碳纳米管和处理过的碳纳米管作为包封层制备了具有空间约束的镍基催化剂。采用扫描电镜（SEM）、拉曼光谱（Raman spectroscopy）和氮物理吸附（BET）等方法研究了不同处理对碳纳米管长度、结构性能和镍颗粒尺寸的影响。评价了该催化剂对CO2甲烷化反应的催化性能。结果表明，酸氧化-超声处理能显著缩短CNTs的长度。这种长度的减少有助于提高镍颗粒的掺入效率。与未处理的纳米级CNTs相比，混合酸（浓硫酸与浓硝酸体积比为3:1）处理45 min，超声处理2 h后CNTs的平均长度减少到100 nm左右，镍填充效率从34.65%提高到93.84%。酸氧化-超声处理除了可以缩短碳纳米管的长度外，还可以在碳纳米管壁上引入结构缺陷，增加CNTs的孔体积和比表面积，从而促进镍金属在CNTs内的有效包封。CNTs的约束效应成功地将镍的平均粒径从14.92 nm减小到7.14 nm，提高了金属的分散性。结果表明，该催化剂具有较强的CO2甲烷化活性，CO2转化率为79.52%，甲烷选择性为98.98%。

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引用次数: 0

Active species in carbon nanotube nucleation from acetylene: Insights from nanoreactor molecular dynamics 乙炔碳纳米管成核中的活性物质：来自纳米反应器分子动力学的见解

Q3 Energy

燃料化学学报

Pub Date : 2025-12-01 DOI: 10.1016/S1872-5813(25)60573-1

Luotong LI , Tingyu LEI , Jiawei BAI , Xingchen LIU , Botao TENG , Xiaodong WEN

Carbon nanotube formation exemplifies atomically precise self-assembly, where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries. However, elucidating the transient molecular intermediates remains a critical mechanistic frontier. This study investigates the atomic-scale nucleation process of single-walled carbon nanotubes (SWCNTs) from acetylene on iron (Fe) clusters, utilizing GFN-xTB-based nanoreactor molecular dynamics simulations. The simulations reveal a consistent nucleation pathway, regardless of iron cluster size (Fe₁₃, Fe₃₈, Fe₅₅), where the chemisorption and dissociation of acetylene molecules on the Fe clusters lead to the formation of C₂H and C₂ intermediates. These species then undergo oligomerization, initiating the growth of carbon chains. As the chains cross-link and cyclize, five-membered carbon rings are preferentially formed, which eventually evolve into six-membered rings and more complex sp²-hybridized carbon networks, resembling the cap structures of nascent SWCNTs. Although the nucleation mechanism remains similar across all cluster sizes, larger clusters show enhanced catalytic activity, leading to higher molecular weight hydrocarbons and more extensive carbocyclic networks due to their higher density of active sites per reacting molecule. Crucially, the study highlights the role of C₂H as the key active species in the carbon network formation process. These findings offer critical insights into the initial stages of SWCNT nucleation, contributing to a deeper understanding of the mechanisms driving SWCNT growth and guiding the development of optimized synthetic strategies.

碳纳米管的形成体现了原子精确的自组装，其中原子相互作用动态地设计了具有超越经典材料边界的涌现特性的纳米级结构。然而，阐明瞬时分子中间体仍然是一个关键的机制前沿。本研究利用基于gfn - xtb的纳米反应器分子动力学模拟，研究了乙炔单壁碳纳米管（SWCNTs）在铁（Fe）簇上的原子尺度成核过程。模拟结果表明，无论铁簇大小（Fe13, Fe38, Fe55）如何，乙炔分子在铁簇上的化学吸附和解离导致了C2H和C2中间体的形成，形成了一致的成核途径。然后这些物质发生寡聚化，开始碳链的生长。随着碳链的交联和环化，五元碳环优先形成，最终演变成六元环和更复杂的sp2杂化碳网络，类似于新生SWCNTs的帽状结构。尽管所有簇大小的成核机制都是相似的，但更大的簇显示出更强的催化活性，导致更高分子量的碳氢化合物和更广泛的碳环网络，因为每个反应分子的活性位点密度更高。至关重要的是，该研究强调了C2H作为碳网络形成过程中的关键活性物质的作用。这些发现为swcnts成核的初始阶段提供了重要的见解，有助于更深入地了解驱动swcnts生长的机制，并指导优化合成策略的发展。

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引用次数: 0

Effect of lattice distortion of CeO2 on direct synthesis of dimethyl carbonate from CO2 and methanol CeO2晶格畸变对CO2和甲醇直接合成碳酸二甲酯的影响

Q3 Energy

燃料化学学报

Pub Date : 2025-11-01 DOI: 10.1016/S1872-5813(25)60577-9

Jiangtao ZHAO , Peipei AI , Xuyan ZHANG , Xuhao SHAO , Minghui TAN , Wei HUANG

The conversion of CO₂ to dimethyl carbonate (DMC) offers a promising route for CO₂ utilization. In this study, four CeO₂ catalysts with distinct nanostructures were synthesized via a template-free hydrothermal method by systematically varying the types and concentrations of precipitants as well as the hydrothermal reaction conditions, and they were employed for DMC synthesis from CO₂ and methanol. The atomic arrangements of CeO₂ varied significantly with its morphology, leading to differences in lattice distortion, which directly influenced the concentration of oxygen vacancies. Notably, the CeO₂ nanospheres, which exhibited the highest lattice distortion and oxygen vacancy concentration, achieved a DMC yield (11.12 mmol/g) 48 times greater than that of the nanocubes (0.23 mmol/g). The results indicated that oxygen vacancies played a pivotal role in the catalytic process by facilitating the adsorption and activation of CO₂ to form bidentate carbonates, as well as activating methanol to generate methoxy species. These processes collectively promoted the formation of the key intermediate (*CH₃OCOO). This study proposes a strategy to enhance the oxygen vacancy concentration by increasing lattice distortion, providing valuable insights for designing high-performance CeO₂ catalysts for DMC synthesis.

二氧化碳转化为碳酸二甲酯（DMC）为二氧化碳的利用提供了一条很有前途的途径。本研究通过系统地改变沉淀剂的种类和浓度以及水热反应条件，采用无模板水热法合成了四种具有不同纳米结构的CeO2催化剂，并将其用于CO2和甲醇合成DMC。CeO2的原子排列随其形貌的变化而变化，导致晶格畸变的差异，这直接影响了氧空位的浓度。值得注意的是，具有最高晶格畸变和氧空位浓度的CeO2纳米球的DMC产率（11.12 mmol/g）是纳米立方（0.23 mmol/g）的48倍。结果表明，氧空位在催化过程中起关键作用，促进CO2吸附和活化形成双齿碳酸盐，并活化甲醇生成甲氧基物质。这些过程共同促进了关键中间体（*CH3OCOO）的形成。本研究提出了一种通过增加晶格畸变来提高氧空位浓度的策略，为设计用于合成DMC的高性能CeO2催化剂提供了有价值的见解。

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