Journal of CO2 Utilization最新文献_第4页

Interchangeable biogas and CO2 valorization through electrified syngas manufacturing for synthetic fuel production 通过电气化合成气制造用于合成燃料生产的可互换沼气和二氧化碳增值

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-03-01 Epub Date: 2026-01-28 DOI: 10.1016/j.jcou.2026.103331

Thomas N. From , Marené Lobban , Victor B. Terkelsen , Jacobus Visagie , Behzad Partoon , Sebastian T. Wismann , Leon Rens Sander Rosseau , Anders Bentien , Peter.M. Mortensen

To reduce the chemical industry’s strong dependency on fossil-fuels, finding new ways of producing fuels and chemicals based on renewable carbon is a necessity. We demonstrate full-chain, pilot-scale production of renewable synthetic fuel, by converting CO_2, and/or biogas, firstly to syngas and subsequently to syncrude through the Fischer-Tropsch process. Using electrically heated syngas manufacturing at industrially relevant conditions, the CO₂ and biogas were dynamically fed, where steam reforming of CH₄ and reverse water-gas shift of CO₂ and H₂ were achieved interchangeably in the same reactor unit. Dynamic control of the feed gas composition using H₂ and steam allowed for producing syngas with constant composition and, subsequently, enabled stable syncrude production, despite variable inlet concentrations of CH₄ and CO₂. The dynamic control allows for shifting from a net high energy-intensive, hydrogen-consuming, CO₂-based process scheme to a net less energy-intensive CH₄-based process scheme. The interchangeable nature of operation demonstrates that utilization of multiple renewable carbon sources can be integrated with direct electrification of syngas manufacturing, enabling production of synthetic fuels at high capacity with flexible carbon constituent. In addition, this feature enables grid balancing by using stored CH₄, CO₂, or a mixture thereof to regulate plant-scale power offtake through flexible carbon utilization.

为了减少化学工业对化石燃料的严重依赖，必须找到基于可再生碳的新方法来生产燃料和化学品。我们展示了可再生合成燃料的全链中试生产，通过将二氧化碳和/或沼气首先转化为合成气，然后通过费托工艺转化为合成原油。在工业相关条件下，采用电加热合成气制造，动态进料CO2和沼气，其中CH4的蒸汽重整和CO2和H2的逆水气转换在同一反应器单元内交替实现。利用H2和蒸汽对原料气组成进行动态控制，可以生产出成分恒定的合成气，并在进口CH4和CO2浓度变化的情况下实现稳定的合成原油生产。动态控制允许从净高能耗、耗氢、以二氧化碳为基础的工艺方案转变为净低能耗的以ch4为基础的工艺方案。操作的互换性表明，多种可再生碳源的利用可以与合成气制造的直接电气化相结合，从而实现具有灵活碳成分的高容量合成燃料的生产。此外，该特性通过使用储存的CH4、CO2或其混合物，通过灵活的碳利用来调节工厂规模的电力消耗，从而实现电网平衡。

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引用次数: 0

The effect of metal-free synergistic binary deep eutectic solvents based on p-toluenesulfonic acid for efficient CO2 fixation on cyclic carbonates 基于对甲苯磺酸的无金属协同二元深共晶溶剂对环状碳酸盐高效CO2固定的影响

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-03-01 Epub Date: 2026-01-29 DOI: 10.1016/j.jcou.2026.103340

Simin Kafash, Amir Abdolmaleki

A metal-free binary deep eutectic solvent (DES) was prepared from 1-butyl-4-(dimethylamino)pyridinium bromide and p-toluenesulfonic acid (p-TSA). This DES was employed as a liquid catalyst for the cycloaddition of CO₂ to epoxides under mild conditions. The catalyst provides a complementary Brønsted acidic and nucleophilic environment that efficiently promotes the reaction. Under 1 atm CO₂ and 70 ^°C, styrene oxide, considered a challenging substrate, was converted to its cyclic carbonate with 99.6 % conversion and 99.7 % selectivity within 3 h, demonstrating the high efficiency of the catalyst. The DES exhibited good recyclability and maintained its catalytic performance over multiple reaction cycles. Thermal analysis confirmed the notable thermal stability of the DES. The methodology is also applicable to other epoxides, demonstrating high conversions and selectivities. This work highlights the potential of rationally designed DESs as sustainable, recyclable catalysts for CO₂ fixation to cyclic carbonates under mild and practical conditions.

以1-丁基-4-（二甲氨基）溴化吡啶和对甲苯磺酸（p-TSA）为原料制备了一种无金属二元深共晶溶剂（DES）。用该DES作为液体催化剂，在温和条件下催化CO₂与环氧化物的环加成反应。催化剂提供了互补的Brønsted酸性和亲核环境，有效地促进了反应。在1 atm CO₂和70°C条件下，被认为是具有挑战性的底物的氧化苯乙烯在3 h内转化为环状碳酸盐，转化率为99.6 %，选择性为99.7 %，证明了催化剂的高效率。DES具有良好的可回收性，并在多个反应循环中保持催化性能。热分析证实了DES的显著热稳定性。该方法也适用于其他环氧化物，显示出高转化率和选择性。这项工作强调了合理设计的DESs在温和和实用的条件下作为可持续的、可回收的循环碳酸盐固碳催化剂的潜力。

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引用次数: 0

Preparation of high purity CaCO3 by carbonation of carbide slag after physical impurity removal: calcination, cyclone and magnetic separation 电石渣经煅烧、旋流器、磁选等物理除杂后碳化制备高纯碳酸钙

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-03-01 Epub Date: 2026-01-17 DOI: 10.1016/j.jcou.2026.103329

Zhuohui Ma , Wenhao Ning , Huaigang Cheng , Bo Wang

The co-production of high-purity CaCO₃ by carbonating CO₂ from carbide slag (CS) has attracted significant attention. However, due to the complex composition of CS and the difficulty in separating Ca element, it is difficult to balance the carbonation cost and quality of the product. In this study, CS was used as raw material, and a method of preparing high-purity CaCO₃ through calcination, cyclone and magnetic separation, named multi-stage impurity removal, was proposed firstly. The effects of calcination time and temperature on mineral phase transformation and the purity and whiteness of CaCO₃ prepared by carbonation during the calcination of carbide slag were studied. The effects of cyclone and magnetic separations were also discussed. The mechanism for the removal of impurities through high-temperature calcination was discussed innovatively. The optimum process conditions for multi-stage impurity removal and carbonation were determined, after calcination at 900 ℃ for 3 h, the CS was transported to cyclone separation at an inlet volumetric flow rate of 80 m³ /h. The separated substrate was then formulated into a pulp with a S/L of 10 % for magnetic separation. The CS pulp obtained after magnetic separation entered the carbonation process, where it was aerated with CO₂ at a flow rate of 0.2 L/min for carbonation. This process resulted in calcite-type CaCO₃ with the purity and whiteness of 97.8 % and 97.4, respectively. Finally, the cost of the process was estimated. The total initial investment cost was approximately CNY 6.51 million, while the total operating cost was CNY 1915.85/t of CaCO₃.

利用电石渣（CS）碳化CO2联产高纯碳酸钙已引起广泛关注。但由于CS成分复杂，且Ca元素难以分离，难以平衡碳酸化成本和产品质量。本研究以CS为原料，首次提出了一种煅烧-旋风-磁选制备高纯CaCO3的多级除杂方法。研究了煅烧时间和煅烧温度对电石渣煅烧过程中矿物相变及碳化法制备CaCO3纯度和白度的影响。讨论了旋流分离和磁选的影响。创新性地探讨了高温煅烧脱除杂质的机理。确定了多级除杂碳化的最佳工艺条件，经900℃煅烧3 h后，以80 m³ /h的进口体积流量将CS输送到旋风分离器中分离。然后将分离的底物配制成S/L为10 %的纸浆进行磁选。磁选后得到的CS矿浆进入碳酸化过程，以0.2 L/min的流速充入CO2进行碳酸化。该工艺可制得纯度为97.8% %、白度为97.4%的方解石型CaCO3。最后，对该工艺的成本进行了估算。初始投资总成本约651万元，运行总成本为1915.85元/t CaCO3。

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引用次数: 0

Molecular dynamics study on the mechanisms of ultrafine bubbles in CO2 hydrate formation CO2水合物超细气泡形成机理的分子动力学研究

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-03-01 Epub Date: 2026-01-21 DOI: 10.1016/j.jcou.2026.103335

Hamidreza Hassanloo, Xinyan Wang

The accelerating rise in atmospheric CO₂, driven by anthropogenic emissions, necessitates urgent mitigation strategies. Among carbon capture and storage (CCS) technologies, CO₂ hydrate-based methods offer a promising pathway for efficient sequestration, storage, and utilization. However, the inherently slow kinetics of hydrate nucleation and growth limit their practical application. This study explores the use of various nanobubbles (NBs), including hydrogen, nitrogen, oxygen, and carbon dioxide, as stable, nanoscale gas cavities that act as novel promoters to enhance CO₂ hydrate formation, using molecular dynamics (MD) simulations. The results demonstrate that under optimal thermodynamic conditions, the presence of NBs significantly enhances hydrate formation. This enhancement is attributed to the hydrophobic NB surfaces acting as nucleation spots, promoting local concentration gradients and accelerating clathrate formation kinetics, while reducing the likelihood of random nucleation events in the bulk phase. Due to their smaller molecular sizes, hydrogen and nitrogen NBs further facilitate hydrate formation by diffusing into the solution from the NB core. However, lower temperature, as a primary sub-optimal thermal condition, reduce molecular mobility and suppress these mechanisms, thereby hindering hydrate growth. At elevated pressures, NBs exhibit a dual role, both promoting and inhibiting hydrate formation, and the comparison with non-nanobubbled samples reveals a pressure-dependent shift in the dominant nucleation mechanism from NB-induced interfacial ordering to bulk-phase interactions.

由于人为排放导致大气中二氧化碳的加速上升，迫切需要采取减缓战略。在碳捕集与封存（CCS）技术中，以二氧化碳水合物为基础的方法为有效的封存、储存和利用提供了一条有前途的途径。然而，固有的水合物成核和生长缓慢的动力学限制了它们的实际应用。本研究利用分子动力学（MD）模拟，探索了各种纳米气泡（NBs）的使用，包括氢、氮、氧和二氧化碳，作为稳定的纳米级气腔，作为促进CO₂水合物形成的新型促进剂。结果表明，在最佳热力学条件下，NBs的存在显著促进了水合物的形成。这种增强归因于疏水NB表面作为成核点，促进局部浓度梯度和加速笼形物形成动力学，同时减少了体相中随机成核事件的可能性。由于其较小的分子尺寸，氢和氮NB通过从NB核心扩散到溶液中进一步促进水合物的形成。然而，较低的温度作为主要的次优热条件，降低了分子迁移率，抑制了这些机制，从而阻碍了水合物的生长。在高压下，NBs表现出促进和抑制水合物形成的双重作用，与非纳米气泡样品的比较揭示了主要成核机制的压力依赖性转变，从nb诱导的界面有序到体相相互作用。

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引用次数: 0

Phase behavior of binary mixtures of CO2 with methyl, ethyl, and butyl (Phenylacetates) at elevated pressures 二氧化碳与甲基、乙基和丁基（苯乙酸酯）二元混合物在高压下的相行为

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-03-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jcou.2026.103354

Uma Sankar Behera , Jiyun Shim , Hun-Soo Byun

The increasing demand for alkyl phenylacetates, owing to their distinctive characteristics and diverse industrial applications, highlights the necessity of accurate vapor–liquid equilibrium (VLE) data for efficient process design. This is especially crucial in separation processes employing supercritical carbon dioxide (CO₂) as a green solvent. This work deals with the phase transition study of binary mixtures comprising CO₂ and methyl, ethyl, butyl phenylacetate, which was systematically examined within 313.2 K–393.2 K (in 20 K increments) and pressures reaching up to 24.62 MPa. No prior studies have reported detailed isothermal VLE data over such an extensive mole fraction range at elevated pressures for these systems, making this study a unique contribution. Analysis of pressure–temperature behavior indicated that the critical mixture curve connects the critical points of pure CO₂ and each alkyl phenylacetate, consistent with Type-I curve as defined by van Konynenburg and Scott. For all binary systems, solubility improved with increasing phenylacetate concentration, accompanied by a corresponding reduction in system pressure under constant temperature conditions. The experimental bubble point data were fitted using the Peng–Robinson equation of state (PR EoS) combined with the van der Waals one-fluid mixing rule. The interaction (binary) parameters were optimized for each system: methyl phenylacetate (k_ij = 0.028, η_ij = –0.040), ethyl phenylacetate (k_ij = 0.020, η_ij = –0.040), and butyl phenylacetate (k_ij = 0.040, η_ij = –0.045). The PR EoS model exhibited strong agreement with experimental findings, as reflected by root mean square deviation (RMSD%) ranging between 3.82 % and 5.20 % across all three binary systems and studied temperatures.

由于烷基苯乙酸酯的独特特性和不同的工业应用，对其需求不断增加，这突出了准确的汽液平衡（VLE）数据对于有效工艺设计的必要性。这在采用超临界二氧化碳（CO2）作为绿色溶剂的分离过程中尤为重要。这项工作涉及二氧化碳和甲基、乙基、丁基苯乙酸酯二元混合物的相变研究，在313.2 K - 393.2 K（20 K增量）和压力达到24.62 MPa的范围内系统地进行了研究。此前没有研究报道过这些系统在高压下如此广泛的摩尔分数范围内的详细等温VLE数据，这使得这项研究具有独特的贡献。压力-温度行为分析表明，混合临界曲线连接了纯CO2和各苯乙酸烷基的临界点，符合van Konynenburg和Scott定义的i型曲线。在恒温条件下，所有二元体系的溶解度都随着苯乙酸浓度的增加而提高，同时系统压力也相应降低。实验气泡点数据采用Peng-Robinson状态方程（PR EoS）结合范德华单流体混合规则进行拟合。优化了各体系的相互作用（二元）参数：苯基乙酸甲酯（kij = 0.028, ηij = -0.040）、苯基乙酸乙酯（kij = 0.020, ηij = -0.040）和苯基乙酸丁酯（kij = 0.040, ηij = -0.045）。PR - EoS模型与实验结果非常吻合，这反映在所有三个双星系统和研究温度的均方根偏差（RMSD%）在3.82 %和5.20 %之间。

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引用次数: 0

Carbon dioxide capture from air in buildings – Design and techno-economic feasibility of practical systems 建筑物中空气中的二氧化碳捕获。实用系统的设计和技术经济可行性

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-03-01 Epub Date: 2026-02-13 DOI: 10.1016/j.jcou.2026.103351

Dominik Heß, Michael Rubin, Roland Dittmeyer

Direct Air Capture (DAC) is needed alongside other CO₂ removal methods to ensure that the total amount of CO₂ required is removed from the atmosphere so that global warming can be limited to below 2 °. While large-scale DAC farms are a promising solution, their high CAPEX and OPEX, along with societal concerns, may hinder widespread deployment. This study presents a novel, modular DAC concept designed for integration into heating, ventilation, and air conditioning (HVAC) systems of buildings. A prototype was engineered and modeled in MATLAB to analyze key physical processes in the adsorber bed using two amine-based adsorbents. A linear driving force model was applied to simulate mass transport, and the DAC unit was coupled with an HVAC system in Simulink to evaluate CO₂ capture from indoor air. Solar thermal energy with thermal storage was defined as the heat source. Optimization results indicate a 40 % reduction in thermal energy demand compared to separate DAC and HVAC systems. Cold, humid air improves CO₂ capture, while dry air significantly lowers the energy demand – up to 50 % when reducing humidity from 90 % to 10 %. A techno-economic analysis suggests that mass-produced DAC modules for HVAC systems could achieve levelized costs of DAC as low as 280 € per ton CO₂, particularly when waste heat is utilized. Implementation in densely occupied buildings may yield additional savings of up to 9 %. This work highlights the potential of HVAC-integrated DAC systems as a scalable, cost-effective complement to centralized DAC facilities.

直接空气捕获（DAC）与其他二氧化碳去除方法一起需要，以确保从大气中去除所需的二氧化碳总量，从而将全球变暖限制在2°以下。虽然大型DAC农场是一个很有前途的解决方案，但它们的高资本支出和运营成本，以及社会问题，可能会阻碍广泛部署。本研究提出了一种新颖的模块化DAC概念，旨在将其集成到建筑物的供暖、通风和空调（HVAC）系统中。设计了一个原型，并在MATLAB中建模，分析了两种胺基吸附剂在吸附床中的关键物理过程。采用线性驱动力模型模拟质量输运，并在Simulink中将DAC单元与暖通空调系统耦合，以评估从室内空气中捕获的CO₂。热源定义为蓄热的太阳能。优化结果表明，与单独的DAC和HVAC系统相比，热能需求减少了40% %。寒冷潮湿的空气改善了CO₂的捕获，而干燥的空气显著降低了能源需求-当湿度从90% %降低到10% %时，能源需求可降低50% %。一项技术经济分析表明，大规模生产用于HVAC系统的DAC模块可以实现DAC的平均成本低至每吨二氧化碳280欧元，特别是在利用废热的情况下。在人口密集的建筑物中实施可能会产生高达9 %的额外节省。这项工作突出了hvac集成DAC系统作为集中式DAC设施的可扩展、经济有效补充的潜力。

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引用次数: 0

Kinetic and catalytic evaluation of a stable and selective Zn-Cr/KIT-6 catalyst for propane dehydrogenation using CO2 as a mild oxidant 以CO2为温和氧化剂的稳定选择性Zn-Cr/KIT-6丙烷脱氢催化剂的动力学和催化评价

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-02-01 Epub Date: 2026-01-06 DOI: 10.1016/j.jcou.2025.103311

Hanieh Habibpoor, Majid Taghizadeh

The oxidative dehydrogenation (ODH) of propane using CO₂ as a soft oxidant represents a promising strategy for selective propylene production alongside effective CO₂ valorization, emphasizing the critical need for highly active and stable catalysts. In this work, a series of Cr-based catalysts with chromium loadings ranging from 3 to 10 wt% were synthesized via the incipient-wetness impregnation method, employing three-dimensional mesoporous silica KIT-6 as the support. The catalysts were further modified by zinc promotion to enhance catalytic performance in the CO₂-ODP. Comprehensive physicochemical characterization-including XRD, FT-IR, SEM, EDX elemental mapping, HRTEM, N₂ physisorption, H₂-TPR, NH₃-TPD, CO₂-TPD, XPS, Raman and TGA-confirmed that the ordered 3D mesoporous structure of KIT-6 was retained post-metal impregnation, facilitating superior dispersion of chromium oxide species. Among the prepared catalysts, 7 %Cr/KIT-6 exhibited optimal propane conversion and propylene selectivity. Zinc promotion significantly enhanced the chromium-support interaction and increased the surface concentration of highly oxidizing Cr^6 + species, which plays a crucial role in improving catalytic activity for the propane dehydrogenation reaction. The 1.5 %Zn-7 %Cr/KIT-6 catalyst exhibited initially superior performance at 550 °C, achieving 50.7 % propane conversion, with propylene selectivity and yield of 79.9 % and 40.5 %, respectively. Kinetic studies based on the Langmuir-Hinshelwood model effectively described the reaction mechanism over the promoted catalyst. The estimated apparent activation energy (

E_{a p p}^{c a t}

= 83.98 kJ·mol⁻¹) indicates that the dehydrogenation proceeds rapidly and more easily in the presence of this catalyst.

使用CO2作为软氧化剂对丙烷进行氧化脱氢（ODH）是一种很有前途的选择性丙烯生产策略，同时还能有效地使CO₂增值，强调了对高活性和稳定催化剂的迫切需求。本研究以三维介孔二氧化硅KIT-6为载体，采用初湿浸渍法合成了一系列cr基催化剂，其载铬量为3 ~ 10 wt%。采用锌促进法对催化剂进行进一步改性，提高了催化剂在CO2-ODP中的催化性能。综合理化表征——包括XRD、FT-IR、SEM、EDX元素图、HRTEM、N2物理吸附、H2-TPR、NH3-TPD、CO2-TPD、XPS、Raman和tga——证实了KIT-6在金属浸渍后仍保持有序的三维介孔结构，有利于氧化铬的优异分散。制备的催化剂中，7 %Cr/KIT-6具有最佳的丙烷转化率和丙烯选择性。锌的促进作用显著增强了铬载体的相互作用，提高了高氧化性Cr6 +的表面浓度，这对丙烷脱氢反应的催化活性起着至关重要的作用。1.5 %Zn-7 %Cr/KIT-6催化剂在550℃时表现出优异的性能，丙烷转化率为50.7% %，丙烯选择性和产率分别为79.9% %和40.5 %。基于Langmuir-Hinshelwood模型的动力学研究有效地描述了催化剂上的反应机理。表观活化能（Eappcat = 83.98 kJ·mol−1）表明，在该催化剂的存在下，脱氢反应进行得更快、更容易。

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引用次数: 0

Synthesis and evaluation of bifunctional reforming-shift composite catalysts on metal foams for methanol steam reforming with reduced CO production 金属泡沫双功能重整-移位复合催化剂的合成与评价

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-02-01 Epub Date: 2026-01-10 DOI: 10.1016/j.jcou.2026.103323

S. Gorji , S. Zarrinpashne , A. Zamaniyan , N. Mostoufi , H. Kiarad

This study investigates a strategy to reduce carbon monoxide (CO) content in the product gas from methanol steam reforming, a critical challenge since CO acts as a poison for fuel cell catalysts. To achieve this, bifunctional catalysts were developed on metallic foams. Bifunctional catalysts consisting of a leading layer of reforming catalyst composed of Cu/Zn/Zr oxides, followed by a low temperature water-gas shift (LTS) catalyst layer composed of Cu/Zn oxides, were synthesized over copper and nickel foams that were precoated with a thin layer of Al₂O₃. The effects of foam material, catalyst loading, share of LTS layer, reactor temperature, feed space velocity and steam to carbon ratio were studied on the performance of the catalyst in a microreactor system regarding methanol conversion, specific hydrogen (H₂) production rate and CO content of the product gas. The bifunctionalization approach proved highly effective, achieving over 70 % reduction in CO production, corresponding to a CO content in the product gas of less than 0.4 vol%, accompanied by no significant loss in methanol conversion. The bifunctional catalyst exhibited superior activity at lower temperatures, enhanced long term performance and higher specific H₂ production compared to similar studies on mono-functional reforming catalysts. It may be considered as a step forward in portable H₂ generator systems via steam reforming of methanol, with a more compact size and less CO production.

本研究探讨了一种降低甲醇蒸汽重整产物气体中一氧化碳（CO）含量的策略，这是一项关键挑战，因为一氧化碳对燃料电池催化剂来说是一种毒药。为了实现这一目标，在金属泡沫上开发了双功能催化剂。在预涂有Al2O3薄层的铜和镍泡沫表面上，合成了由Cu/Zn/Zr氧化物组成的前置转化催化剂层和由Cu/Zn氧化物组成的低温水气转换（LTS）催化剂层组成的双功能催化剂。研究了泡沫材料、催化剂负载、LTS层份额、反应器温度、进料空速和汽碳比等因素对催化剂在微反应器系统中甲醇转化率、产氢率和产物气体CO含量的影响。双功能化方法被证明是非常有效的，CO产量降低了70% %以上，对应于产品气体中的CO含量低于0.4 vol%，同时甲醇转化没有显著损失。与同类研究的单功能重整催化剂相比，双功能催化剂在低温下表现出更强的活性、更强的长期性能和更高的比H2产率。它可以被认为是便携式氢气发生器系统的一个进步，通过甲醇的蒸汽重整，具有更紧凑的尺寸和更少的CO生产。

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引用次数: 0

Hydrophobicity-guided CO-CO coupling pathways in ZIF-8 modified Cu2O for efficient CO electroreduction ZIF-8修饰Cu2O中疏水引导CO-CO偶联途径的高效CO电还原

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-02-01 Epub Date: 2026-01-06 DOI: 10.1016/j.jcou.2026.103315

Ziyun Xi , Yunyi Xiao , Shuai Luo , Min Liu , Zijun Yan , Runze Bi , Hongling Qin , Cong Wan , Cijie Liu , Tao Wu , Honglei Zhang

The electrochemical CO reduction reaction offered a sustainable approach to convert carbon monoxide into multi-carbon products, yet controlling C-C coupling remained challenging. Herein, we designed a Z-Cu electrocatalyst by coating Cu₂O nanoparticles with ZIF-8, which enabled interfacial modulation of the electronic structure and surface wettability. Structural analyses confirmed strong Cu-Zn interactions, while electrochemical measurements revealed that Z-Cu favored C₂ products at low current densities. Both experimental and DFT calculations demonstrated that Z-Cu suppressed the hydrogenation of *CO into *COH through hydrophobic repulsion and steric hindrance, thereby inhibiting the asymmetric *CO-*COH pathway toward *OCCOH formation. Instead, Z-Cu predominantly facilitated the symmetric *CO-*CO coupling. The optimal enhanced factor of Z-Cu is 5.5 at 50 mA cm⁻². This work underscored the decisive role of hydrophobicity and interfacial electronic modulation in directing CORR pathways, providing new mechanistic insights and a generalizable design principle for advancing Cu-based catalysts toward efficient multi-carbon fuel and chemical production.

电化学CO还原反应为一氧化碳转化为多碳产物提供了一种可持续的方法，但控制C-C耦合仍然是一个挑战。在此，我们设计了一种Z-Cu电催化剂，通过在纳米Cu2O表面涂覆ZIF-8，实现了电子结构和表面润湿性的界面调制。结构分析证实了强的Cu-Zn相互作用，而电化学测量表明，在低电流密度下，Z-Cu有利于C2产物。实验和DFT计算均表明，Z-Cu通过疏水斥力和位阻抑制*CO加氢成*COH，从而抑制了不对称*CO-*COH生成*OCCOH的途径。相反，Z-Cu主要促进了对称的*CO-*CO耦合。在50 mA cm−2时，Z-Cu的最佳增强因子为5.5。这项工作强调了疏水性和界面电子调制在指导CORR途径中的决定性作用，为推进cu基催化剂向高效多碳燃料和化学品生产方向发展提供了新的机制见解和可推广的设计原则。

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引用次数: 0

Encapsulating Cu nanoparticles within MIL-101 for efficient and selective N-methylation of amines using CO2/H2 在MIL-101中封装Cu纳米颗粒，利用CO2/H2有效和选择性地进行胺的n -甲基化

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-02-01 Epub Date: 2026-01-06 DOI: 10.1016/j.jcou.2025.103309

Jianfang Liu, Shuaichong Ding, Li Wang, Weiye Zhang, Lei Wang, Yu Li

The use of CO₂/H₂ for amine N-methylation provides a green and sustainable pathway for CO₂ utilization and the production of N-methylamines. However, the research on advanced catalysts still poses a challenge. Herein, we confined ultrasmall Cu nanoparticles within MIL-101 for catalyzing the N-methylation of amines using CO₂/H₂. When the molar ratio of NaBH₄/Cu was 2:1, the 5 %Cu@MIL-101(Cr) catalyst exhibited excellent catalytic performance and cycling stability. Using cyclohexane as the solvent, under conditions of 4 MPa (P_H2/P_CO2 = 3), and 200 °C for 8 h, the conversion of aniline (AN) reached 94.8 %, with a selectivity of 93.1 % for methylaniline (MA). Benefiting from the confinement effect of the MOF cages, no significant agglomeration of Cu particles was observed in the catalyst after the reaction. The coexistence of Cu⁰-Cu⁺-Cu²⁺ and their synergistic interaction with the Cr–oxo clusters facilitated the high activity of Cu@MIL-101(Cr). Control experiments indicated that CO₂ activated on the Cu⁺ and O²⁻ of the Cr–oxo clusters preferentially reacts with the AN adsorbed on adjacent Cu²⁺ and unsaturated Cr³⁺ sites, forming a phenylcarbamic acid intermediate. This intermediate is subsequently stepwise hydrogenated to MA by spillover H* atoms dissociated on neighboring Cu⁰ sites.

利用CO2/H2进行胺n -甲基化为CO2利用和n -甲胺的生产提供了一条绿色可持续的途径。然而，先进催化剂的研究仍然面临着挑战。在这里，我们将超小的Cu纳米颗粒限制在MIL-101中，用CO2/H2催化胺的n -甲基化。当NaBH4/Cu的摩尔比为2:1时，5 %Cu@MIL-101（Cr）催化剂表现出优异的催化性能和循环稳定性。以环己烷为溶剂，在4 MPa （PH2/PCO2 = 3）、200℃、8 h条件下，苯胺（AN）的转化率达到94.8 %，对甲基苯胺（MA）的选择性为93.1 %。由于MOF笼的约束作用，反应后催化剂中未观察到明显的Cu颗粒团聚现象。Cu0-Cu+-Cu2+的共存及其与Cr - oxo簇的协同作用促进了Cu@MIL-101（Cr）的高活性。对照实验表明，在Cr-oxo簇上活化的CO2优先与吸附在相邻Cu2+和不饱和Cr3+位点上的AN反应，生成苯氨基甲酸中间体。这种中间体随后通过在邻近的Cu0位点上解离的H*原子溢出逐步氢化成MA。

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引用次数: 0