Journal of CO2 Utilization最新文献

Dimensionless automated machine learning for identifying operating correlations in plasma-catalyzed CO2 hydrogenation to CH3OH 用于识别等离子体催化CO2加氢到CH3OH的操作相关性的无量纲自动机器学习

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-10-09 DOI: 10.1016/j.jcou.2026.103587

Daqian Zhu, Yiming Yao, Zeming Zhang, He Zhang, Yunzhu An, Liguang Dou, Shuai Zhang, Cheng Zhang, Jie Pan, Tao Shao

As an emerging route to achieving carbon neutrality, plasma-catalyzed CO₂ hydrogenation to CH₃OH faces challenges in defining suitable operating conditions and achieving industrial implementation. To address these issues effectively, dimensional analysis provides a promising quantitative approach for optimizing such reaction systems. Dimensional analysis enables the extraction of dimensionless numbers from complex physical systems, providing a compact representation of coupled operating variables. This research proposes a dimensionless automated machine learning (AML) framework based on Bayesian optimization (BO) to identify candidate dimensionless groups and empirical operating correlations from heterogeneous literature-derived experimental data. Datasets are constructed by data augmentation and completion for dimensionless analysis. Models built on the selected dimensionless groups achieve a maximum R² of 0.92, and their residuals are centered near zero with a bias of 0.01. The selected dimensionless numbers show clear correlations with CO₂ conversion, CH₃OH selectivity and CH₃OH yield in plasma-catalyzed CO₂ hydrogenation to CH₃OH. Overall, the framework provides compact dimensionless operating maps for methanol-oriented operating-condition screening and offers a quantitative reference for prioritizing conditions in subsequent experiments.

作为实现碳中和的新兴途径，等离子体催化CO2加氢制CH3OH面临着确定合适的操作条件和实现工业实施的挑战。为了有效地解决这些问题，量纲分析为优化这类反应系统提供了一种有前途的定量方法。量纲分析能够从复杂的物理系统中提取无量纲数，提供耦合操作变量的紧凑表示。本研究提出了一种基于贝叶斯优化（BO）的无量纲自动机器学习（AML）框架，用于从异构文献衍生的实验数据中识别候选无量纲组和经验操作相关性。数据集是通过数据扩充和补全来构建的，用于无量纲分析。在所选的无量纲组上建立的模型最大R2为0.92，残差集中在零附近，偏差为0.01。所选择的无因次数与等离子体催化CO2加氢制CH3OH的CO2转化率、CH3OH选择性和CH3OH产率有明显的相关性。总体而言，该框架为面向甲醇的工况筛选提供了紧凑的无量纲操作图，并为后续实验中优选工况提供了定量参考。

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引用次数: 0

Outstanding performance of low-metal-content Rh/Al2O3 catalysts structured on metallic substrates in the dry and combined reforming of methane 金属基质结构低金属含量Rh/Al2O3催化剂在甲烷干重整和组合重整中表现优异

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-10-09 DOI: 10.1016/j.jcou.2026.103589

Andrea Navarro-Puyuelo, Inés Reyero, Oihane Sanz, Fernando Bimbela, Mario Montes, Luis M. Gandía

Low-Rh-loading (0.15 wt%) alumina-supported catalysts structured on FeCrAl alloy monoliths and foams with different cell densities and porosities were developed for the dry and combined (O₂-fed) reforming of methane at 700 °C and 150 N L CH₄·(g_cat·h)⁻¹. A facile all-in-one slurry formulation was used to washcoat the substrates. In both dry and combined reforming, foam-based catalysts achieved higher CH₄ and CO₂ conversions as well as higher H₂ and CO yields than parallel-channel monoliths. For dry reforming, substrates with the lowest cell densities and, consequently, the highest porosities, produced the most active dry reforming catalysts. This behavior was attributed to their lower volumetric thermal conductivities, which likely provide more favourable operating conditions for this highly endothermic reaction. In contrast, performance differences among structured catalysts were less pronounced in combined reforming, owing to its lower net thermal demand resulting from the contribution of exothermic methane oxidation. Foam-structured catalysts exhibited an excellent balance between CH₄ and CO₂ conversions at space velocities, normalized per mole of active metal, more than two orders of magnitude higher than those reported for the most active catalyst in the literature. These results demonstrate the strong potential of low-Rh-loading structured catalysts for the development of industrially relevant methane and biogas reforming technologies.

在700℃和150 N L CH4·（gcat·h）−1条件下，制备了低铑负载（0.15 wt%）的铝负载催化剂（FeCrAl合金整体和不同孔密度和孔隙率的泡沫结构），用于甲烷的干式和复合（o2供气）重整。采用一种简便的一体化浆料配方对基材进行洗涂。在干燥重整和组合重整中，泡沫基催化剂比平行通道单体催化剂具有更高的CH4和CO2转化率以及更高的H2和CO产率。对于干重整，具有最低细胞密度的底物，因此，孔隙率最高，产生最活跃的干重整催化剂。这种行为归因于它们较低的体积热导率，这可能为这种高度吸热反应提供了更有利的操作条件。相比之下，在组合重整中，由于放热甲烷氧化的贡献，其净热需求较低，因此结构催化剂之间的性能差异不太明显。泡沫结构催化剂在每摩尔活性金属标准化的空速下表现出良好的CH4和CO2转化平衡，比文献中报道的最活性催化剂高出两个数量级以上。这些结果表明，低铑负载的结构催化剂在工业相关的甲烷和沼气转化技术的发展中具有强大的潜力。

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引用次数: 0

NADH-recycling and NADH-free strategies for formate dehydrogenase-driven electrocatalytic CO2 reduction 甲酸脱氢酶驱动的电催化CO2还原的nadh回收和无nadh策略

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-10-02 DOI: 10.1016/j.jcou.2026.103583

Jiin Choi, Yerin Bang, Keerthana Shanmuganathan, Sieun Kim, Seung-Ryong Kwon, Seol Baek

Formate dehydrogenases (FDHs) are highly selective and sustainable biocatalysts for the electrochemical reduction of carbon dioxide (CO₂) to formate, a promising energy carrier and industrial feedstock. However, the requirement for costly NADH, i.e., the reduced form of nicotinamide adenine dinucleotide (NAD⁺), as a cofactor, combined with the relatively sluggish kinetics of NAD-dependent FDHs for CO₂ reduction, remains a significant bottleneck for their large-scale industrial implementation. To address these limitations, this review examines two main strategies. The first focuses on efficient NADH regeneration via photocatalytic, enzymatic, and electrochemical approaches in enzymatic CO₂ reduction systems, thereby reducing overall NADH consumption. The second explores NADH-independent solutions, including the replacement of natural NADH with artificial cofactors, often supported by synergistic strategies such as enzyme immobilization and electron transfer pathway engineering. This approach also involves the development of cofactor-free, direct electron transfer (DET) systems enabled by electrode-enzyme engineering for NAD-independent FDHs. Collectively, these strategies hold promise for overcoming the economic and mechanistic bottlenecks of FDH-based electrocatalytic CO₂ reduction. Insights gained via a more detailed understanding of FDH-catalyzed CO₂ reduction mechanisms are expected to provide valuable guidance for the future design of efficient, scalable, and sustainable CO₂ reduction technologies.

甲酸脱氢酶（FDHs）是一种高选择性和可持续的生物催化剂，用于电化学还原二氧化碳（CO2）生成甲酸，是一种很有前途的能源载体和工业原料。然而，需要昂贵的NADH，即烟酰胺腺嘌呤二核苷酸（NAD+）的还原形式，作为辅助因子，再加上NADH依赖性FDHs对CO2还原的相对缓慢的动力学，仍然是其大规模工业实施的重大瓶颈。为了解决这些限制，本文审查了两种主要策略。第一个重点是通过光催化、酶和电化学方法在酶促CO2还原系统中有效地再生NADH，从而减少总体NADH消耗。第二部分探讨了与NADH无关的解决方案，包括用人工辅助因子替代天然NADH，通常由酶固定化和电子转移途径工程等协同策略支持。这种方法还涉及到通过电极酶工程实现无辅助因子、直接电子转移（DET）系统的开发，该系统可用于不依赖nada的fdh。总的来说，这些策略有望克服基于fdh的电催化二氧化碳还原的经济和机制瓶颈。通过更详细地了解fdh催化的二氧化碳减排机制，预计将为未来设计高效、可扩展和可持续的二氧化碳减排技术提供有价值的指导。

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引用次数: 0

An integrated assessment of CO₂ mineralization storage potential, injectivity, and source–sink matching in Changbai Mountain Basalts, Northeast China 长白山玄武岩CO 2矿化储存潜力、注入性及源汇匹配综合评价

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-10-06 DOI: 10.1016/j.jcou.2026.103584

Lianghan Cong, Zhihao Gao, Shijia Ma, Shuaiyi Lu, Pan Jiang, Long Wang, Xiaoshu Lü

Basalt mineralization offers durable CO₂ storage, yet regional assessments remain sensitive to formation geometry, connected pore volume and injection mobility. We present a regional screening assessment of the Changbai Mountain basalts in Northeast China. Among the assessed units, the Junjianshan Formation is the most promising because of its mafic composition, locally substantial thickness and vesicular–fractured character. A 100,000-realisation Monte Carlo analysis using formation-specific thickness and basalt-analogue connected-porosity and carbonate-occupancy distributions gives 0.14–0.45 Mt CO₂ km⁻² (P10–P90; median 0.27 Mt km⁻²). Mapping products delineate different geological footprints; separate 100, 200 and 400 km² assessed-area scenarios therefore give 0.014–0.181 Gt across the combined P10–P90 range. A transient line-source model gives 0.006–0.162 Mt CO₂ yr⁻¹ per well at the reference relative permeability across 5–150 mD, and precipitation sensitivities reduce the 50 mD reference rate from 0.057 to 0.036–0.050 Mt yr⁻¹ . Pressure, geomechanical, water, cost and logistics screens define the measurements required for site appraisal.

玄武岩矿化提供持久的CO₂储存，但区域评估仍然对地层几何形状、连通孔隙体积和注入流动性敏感。对东北长白山玄武岩进行了区域筛选评价。在评价单元中，军尖山组因其基性组成、局部厚度和囊状裂缝特征而最有潜力。一项包含10万数据的蒙特卡罗分析使用了特定地层的厚度和玄武岩-类似的连通孔隙度和碳酸盐-占用分布，得出了0.14-0.45 Mt CO₂km⁻²（P10-P90；中位数0.27 Mt km⁻²）。映射产品描述不同地质的足迹;因此，在综合的P10-P90范围内，分别为100、200和400 km²的评估面积情景给出0.014-0.181 Gt。瞬态线源模型在5-150 mD的参考相对渗透率下给出0.006-0.162 Mt CO₂yr -每口井的毒血症，而沉淀敏感性将50 mD的参考率从0.057降低到0.036-0.050 Mt yr -毒血症 。压力、地质力学、水、成本和物流屏幕定义了现场评估所需的测量。

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引用次数: 0

Assessing biogenic carbon dioxide resource for synthetic e-fuel production to decarbonise shipping 评估用于合成电子燃料生产的生物二氧化碳资源，以使航运脱碳

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-09-29 DOI: 10.1016/j.jcou.2026.103582

Asif Tanvir Bhuiya, Nathan Gray, Richard O'Shea, Anga Hackula, Soumitra Pati, Archishman Bose, David M. Wall, Jerry D. Murphy

A high-level assessment of the production potential and costs of three synthetic e-fuels, methane, methanol and Fischer–Tropsch diesel, derived from renewable hydrogen and biogenic carbon dioxide (CO₂) was conducted for maritime transport in the EU and Ireland for 2050. Biogenic CO₂ sources included by-products from biomethane production and ethanol fermentation (priced at €30/tonne), and emissions from biomass combustion (€80/tonne). Direct air carbon capture (€400/tonne) was assessed as a supplementary carbon source. The analysis evaluates CO₂ availability, fuel production potential, hydrogen and electrolysis requirements, and levelised fuel costs relative to projected maritime energy demand of 705 TWh in the EU and 3.86 TWh in Ireland. Based on the assumptions used, total theoretical biogenic CO₂ enables methane and methanol production exceeding projected EU maritime energy demand. In contrast, Fischer–Tropsch diesel production potential from biogenic CO₂ yields only 59% of projected demand, requiring supplementary direct air carbon capture. Methanol recorded the lowest modelled levelised production cost at €113/MWh. Fischer–Tropsch diesel was significantly more expensive (€312/MWh) due to higher hydrogen and CO₂ requirements, lower carbon utilisation and broader product distribution. Biogenic CO₂ availability for the maritime sector may decrease due to competition from other sectors, such as aviation, and limited access to point sources. If the biogenic CO₂ resource available to maritime falls to 50% for methanol or 40% for methane, direct air carbon capture becomes necessary to meet EU maritime fuel demand. The findings demonstrate how CO₂ source, cost and availability influence synthetic maritime fuel production potential and costs.

对三种合成电子燃料（甲烷、甲醇和费托柴油）的生产潜力和成本进行了高级评估，这三种燃料来自可再生氢和生物二氧化碳（CO2），用于2050年欧盟和爱尔兰的海上运输。生物源二氧化碳来源包括生物甲烷生产和乙醇发酵的副产品（价格为每吨30欧元），以及生物质燃烧的排放（每吨80欧元）。直接空气碳捕获（400欧元/吨）被评估为补充碳源。该分析评估了二氧化碳的可用性、燃料生产潜力、氢气和电解需求，以及相对于预计的705 太瓦时（欧盟）和3.86 太瓦时（爱尔兰）的海上能源需求的燃料成本。根据所使用的假设，总理论生物二氧化碳使甲烷和甲醇的产量超过预计的欧盟海洋能源需求。相比之下，从生物源二氧化碳中提取的费托柴油生产潜力仅为预计需求的59%，需要补充直接空气碳捕获。甲醇的模型化生产成本最低，为113欧元/兆瓦时。费托柴油的成本要高得多（312欧元/兆瓦时），原因是氢气和二氧化碳的需求更高，碳利用率更低，产品分销范围更广。由于来自其他部门（如航空）的竞争以及对点源的有限获取，海洋部门的生物源二氧化碳可用性可能会减少。如果海洋可用的生物源二氧化碳资源中甲醇的比例降至50%，甲烷的比例降至40%，那么直接的空气碳捕获就有必要满足欧盟的海上燃料需求。研究结果表明，二氧化碳的来源、成本和可用性如何影响合成海上燃料的生产潜力和成本。

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引用次数: 0

Conceptual process design for producing electro-sustainable aviation fuel (e-SAF) from carbon dioxide and green hydrogen 从二氧化碳和绿色氢中生产电可持续航空燃料（e-SAF）的概念工艺设计

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-10-08 DOI: 10.1016/j.jcou.2026.103586

Sheng-Chi Lien, Tzu-Wei Wang, Zhen-Xian Dai, Chong Wei Ong, Shu-Yu Lin, Wei-Jyun Wang, Jeffrey Chi-Sheng Wu, Cheng-Liang Chen

This study investigates the production of synthetic crude oil (syncrude) as an intermediate for producing electro-sustainable aviation fuel (e-SAF) utilizing captured carbon dioxide (CO₂) and hydrogen (H₂) from green electricity electrolysis via Fischer-Tropsch (FT) synthesis. A process model was developed using Aspen Plus®, integrating the steam reforming (STR), the reverse water-gas shift (RWGS), and the FT reaction units to evaluate the technical feasibility of the syncrude production. The syncrude is upgraded via hydrogenation (HG) to saturate olefins into stable alkanes, followed by two distillation columns for product fractionation. The primary e-SAF components (C₇-C₁₆) are subjected to isomerization to meet the freezing point specifications, while the heavy waxes (C₁₆⁺) are processed in a hydrocracking (HC) reactor and recycled back to the distillation column to enhance yield of C₇-C₁₆ hydrocarbons. The light hydrocarbons C₁–C₅ (C₆-) recovered from the distillation columns and the FT reactor are directed to the STR reactor to regenerate syngas. At a base-case electricity price of 30 $/MWh, the levelized e-SAF production cost is estimated at 1133 $/kL, approximately 86% higher than that of conventional jet fuel. Overall, the proposed pathway provides a technically viable route for e-SAF production with the potential to reduce the carbon intensity of aviation fuels and contribute to aviation decarbonization.

本研究研究了合成原油（syncrude）的生产，作为生产电可持续航空燃料（e-SAF）的中间体，利用绿色电力电解通过费托合成（FT）捕获的二氧化碳（CO₂）和氢（H2）。利用Aspen Plus®开发了一个过程模型，整合了蒸汽重整（STR）、逆向水气变换（RWGS）和FT反应单元，以评估合成原油生产的技术可行性。合成原油通过加氢（HG）将烯烃饱和为稳定的烷烃，然后通过两个精馏塔进行产品分馏。e-SAF主要组分（C7-C16）进行异构化以满足凝固点要求，而重蜡（C₁6⁺）在加氢裂化（HC）反应器中进行处理，然后再循环回精馏塔，以提高C7-C16碳氢化合物的收率。从精馏塔和FT反应器中回收的轻烃C1-C5 （C6-）被导向STR反应器再生合成气。在基本电价为30美元/兆瓦时的情况下，电子saf的平准化生产成本估计为1133美元/千升，比传统航空燃料高出约86%。总的来说，所提出的途径为e-SAF的生产提供了一条技术上可行的途径，具有降低航空燃料碳强度和促进航空脱碳的潜力。

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引用次数: 0

High-temperature calcination-induced Cu–Al–O precursor environments enable accessible Cu sites in Cu/Al2O3 catalysts for the reverse water–gas shift reaction 高温煅烧诱导的Cu - al - o前驱体环境使Cu/Al2O3催化剂中的Cu位点可达，用于逆向水气转换反应

IF 8.6 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-10-01 Epub Date: 2026-10-03 DOI: 10.1016/j.jcou.2026.103585

Dojun Kim, Gang Min Lee, Hye Sun Shin, Cheonwoo Jeong, Chungwoo Lee, Myung-gi Seo, Kwan-Young Lee

High-temperature calcination was investigated as a precursor-engineering strategy to enhance Cu-site accessibility in Cu/Al₂O₃ catalysts for the reverse water–gas shift reaction. Cu/Al₂O₃ catalysts with different Cu loadings were calcined at 950 °C, and a 15 wt% Cu catalyst calcined at 600 °C was prepared for comparison. Although 950 °C calcination decreased the specific surface area, XRD, Raman spectroscopy, and H₂-TPR showed that it diminished crystalline CuO-like features and generated strongly interacting Cu–Al–O precursor environments. After H₂ reduction, 15Cu/Al₂O₃(950 °C) exhibited weaker metallic Cu reflections and less localized Cu-containing domains than 15Cu/Al₂O₃(600 °C). N₂O titration further revealed that 15Cu/Al₂O₃(950 °C) had the highest N₂O consumption of 47.5 μmol g_cat⁻¹, approximately 4.2 times higher than that of 15Cu/Al₂O₃(600 °C), indicating a larger population of accessible N₂O-reactive reduced Cu sites. Consequently, 15Cu/Al₂O₃(950 °C) showed the highest CO₂ conversion at 500 °C under the screening conditions while maintaining approximately 100% CO selectivity. Under the high-space-velocity conditions used for kinetic analysis, however, this catalyst exhibited a moderately higher apparent activation energy (35.7 vs. 27.2 kJ mol⁻¹) and lower site-normalized TOFs than 15Cu/Al₂O₃(600 °C). Its higher mass-normalized activity at 500 °C is therefore attributed to its approximately 4.2-fold larger population of accessible Cu sites, which more than compensated for its lower activity per accessible site.

研究了高温煅烧作为提高Cu/Al2O3催化剂中Cu位点可达性的前驱体工程策略。在950 ℃下煅烧不同Cu负载的Cu/Al2O3催化剂，并制备了600 ℃下煅烧15 wt% Cu催化剂进行比较。虽然950 °C煅烧降低了比表面积，但XRD、拉曼光谱和H2-TPR表明，煅烧降低了cuo类晶体特征，并产生了强相互作用的Cu-Al-O前驱体环境。H2还原后，15Cu/Al2O3（950 °C）比15Cu/Al2O3（600 °C）表现出更弱的金属Cu反射和更少的局部含Cu畴。N2O滴定进一步表明，15Cu/Al2O3（950 °C）的N2O消耗最高，为47.5 μmol gcat−1，约为15Cu/Al2O3（600 °C）的4.2倍，表明可接近的N2O反应还原Cu位点数量更多。因此，在筛选条件下，15Cu/Al2O3（950 °C）在500 °C时表现出最高的CO2转化率，同时保持约100%的CO选择性。然而，在用于动力学分析的高空速条件下，与15Cu/Al2O3（600 °C）相比，该催化剂表现出较高的表观活化能（35.7 vs. 27.2 kJ mol−1）和较低的位标准化TOFs。因此，它在500 °C时较高的质量归一化活性归因于其可达铜位的数量约为4.2倍，这远远弥补了其每个可达位的较低活性。

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引用次数: 0

Bridging molecular interactions and macroscopic thermodynamics in deep eutectic solvents for CO₂ capture 桥接分子相互作用和宏观热力学在深共晶溶剂CO₂捕获

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-06-01 Epub Date: 2026-05-25 DOI: 10.1016/j.jcou.2026.103456

Alberto Gutiérrez , Hoda Moslehi , Santiago Aparicio , Sayed Mostafa Hosseini

Deep eutectic solvents (DESs) offer a sustainable route to low-energy CO₂ capture owing to their tunable structure, low volatility, and recyclability. However, establishing clear relationships between molecular structure, thermophysical behaviour, and gas solubility remains essential for the rational design of next-generation DES-based capture systems. In this work, we integrate semi-empirical modeling with molecular dynamics (MD) simulations to describe the thermophysical properties and CO₂ solubility of three prototypical DESs—Reline, Glyceline, and Ethaline. A perturbed hard-sphere equation of state (PHS EoS) was applied to predict density, compressibility, and viscosity up to 100 MPa, while a revised μ–μ framework was used to correlate CO₂ solubilities over the temperature range 303–343 K. The PHS EoS provided accurate predictions of thermophysical properties, and the revised μ–μ model reproduced CO₂ solubilities with deviations below 10%. MD simulations revealed stable hydrogen-bond networks that promote CO₂ retention through a combination of physical and chemical interactions. Overall, this integrated and data-efficient approach bridges molecular-scale structure and macroscopic thermodynamics, providing a rational pathway for designing environmentally benign solvents for carbon capture and green separation processes.

深共晶溶剂（DESs）由于其可调的结构、低挥发性和可回收性，为低能耗的二氧化碳捕获提供了一条可持续的途径。然而，建立分子结构、热物理行为和气体溶解度之间的明确关系对于合理设计下一代基于des的捕获系统仍然至关重要。在这项工作中，我们将半经验模型与分子动力学（MD）模拟相结合，描述了三种原型DESs-Reline、Glyceline和Ethaline的热物理性质和CO 2溶解度。采用微动硬球状态方程（PHS EoS）预测了100 MPa范围内的密度、可压缩性和粘度，采用修正的μ -μ框架预测了303-343 K温度范围内的CO₂溶解度。PHS EoS提供了准确的热物理性质预测，修正后的μ -μ模型再现了CO₂溶解度，偏差小于10%。MD模拟显示，稳定的氢键网络通过物理和化学相互作用的组合促进CO₂潴留。总体而言，这种集成且数据高效的方法将分子尺度结构与宏观热力学联系起来，为设计环境友好的碳捕获溶剂和绿色分离过程提供了合理的途径。

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引用次数: 0

Mechanistic insights into defect-mediated Cu-CrO2 interfaces for selective CO2 electroreduction to ethanol 缺陷介导的Cu-CrO2界面对选择性CO2电还原乙醇的机理研究

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-06-01 Epub Date: 2026-05-26 DOI: 10.1016/j.jcou.2026.103469

Masoud Safari Yazd , Mohammadreza Omidkhah , Mahmoud Moharrami , Farshid Sobhani Bazghaleh , Hamidreza Rahmani , Azam Akbari

The selective CO₂ electroreduction (CO₂RR) into multi-carbon oxygenates represents a promising route toward carbon-neutral fuel synthesis but remains challenged by poor selectivity and high energy barriers on conventional Cu catalysts. Here, we design a defect-engineered Cu-CrO₂ (CCr) catalyst that exhibits a moderate metal-support interaction (MSI) capable of tuning the surface electronic structure, facilitating charge transfer, and stabilizing key oxygenated intermediates. Experimental and theoretical analyses reveal the cooperative role of CrO₂ in modulating Cu’s redox behavior and oxygen-vacancy chemistry. XPS and O 1 s spectra demonstrate a threefold increase in reduced Cu⁰&Cu⁺ species and an O_V/O_L ratio of 2.3, while DRS shows band-gap narrowing from 2.9 to 2.2 eV, evidencing interfacial charge delocalization. DFT calculations confirm that the Cu-CrO₂ interface lowers interfacial interaction energy (E_int = 8002 cal mol⁻¹) relative to Cu-CuO₂ (8212 cal mol⁻¹) and promotes defect-assisted charge transfer across Cu-O-Cr linkages. Electrochemical measurements demonstrate a lower onset potential (-0.88 V vs Ag/AgCl) and smaller overpotential (0.64 V) for CCr, together with a C₂ Faradaic efficiency of 78.5% and an exceptional ethanol selectivity of 52.9%, compared to 27.4% for Cu. DFT-derived energy maps show that CrO₂ promotion deepens the thermodynamic stabilization (ΔE ≪ 0) of oxygen-retaining intermediates, thereby redirecting the reaction network from C-O bond cleavage (ethylene) to O-retaining hydrogenation (ethanol). Together, experiment and computation establish that defect-mediated moderate MSI, realized through Cu-CrO₂ interfacial coupling, optimizes charge transport, accelerates proton-coupled electron transfer (PCET), and selectively stabilizes oxygenates. This mechanistic insight provides a general design strategy for engineering oxide-promoted Cu catalysts that achieve efficient, durable, and ethanol-oriented CO₂ electroreduction.

选择性CO2电还原（CO2RR）制备多碳氧合物是碳中性燃料合成的一条很有前途的途径，但传统Cu催化剂的选择性差和高能量势垒仍然存在挑战。在这里，我们设计了一种缺陷工程Cu-CrO2 （CCr）催化剂，该催化剂表现出适度的金属-载体相互作用（MSI），能够调节表面电子结构，促进电荷转移，并稳定关键的氧化中间体。实验和理论分析表明，CrO2在Cu的氧化还原行为和氧空位化学中起协同调节作用。XPS和O 1 s光谱显示cu0和Cu+的还原态增加了三倍，OV/OL比为2.3，而DRS显示带隙从2.9缩小到2.2 eV，表明界面电荷离域。DFT计算证实，相对于Cu-CuO2(8212 cal mol−1)，Cu-CrO2界面降低了界面相互作用能（Eint = 8002 cal mol−1），促进了Cu-O-Cr键间缺陷辅助电荷转移。电化学测量表明，CCr具有较低的起始电位（-0.88 V vs Ag/AgCl）和较小的过电位（0.64 V）， C2法拉第效率为78.5%，乙醇选择性为52.9%，而Cu为27.4%。dft衍生的能量图显示，CrO2的促进加深了保氧中间体的热力学稳定性（ΔE ≪ 0），从而将反应网络从C-O键裂解（乙烯）转向保氧加氢（乙醇）。实验和计算表明，通过Cu-CrO2界面耦合实现的缺陷介导的中等MSI优化了电荷传输，加速了质子耦合电子转移（PCET），并选择性地稳定了氧合物。这种机制的洞察为实现高效、耐用和乙醇导向的CO2电还原的工程氧化物促进Cu催化剂提供了一般设计策略。

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引用次数: 0

Heterogeneous cerium phosphate catalyst for the alternating copolymerization of carbon dioxide and epoxide 二氧化碳与环氧化物交替共聚的多相磷酸铈催化剂

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization

Pub Date : 2026-06-01 Epub Date: 2026-05-25 DOI: 10.1016/j.jcou.2026.103461

Masayoshi Honda, Hiroshi Sugimoto

Rare-earth phosphate was found to be an effective catalyst for the alternating copolymerization of carbon dioxide (CO₂) and epoxide. This is a first report of completely inorganic heterogeneous catalyst for this reaction even in the absence of any solvent. Among various rare-earth phosphates, cerium phosphate showed the highest activity in the reaction of CO₂ and propylene oxide and gave poly(propylene carbonate) (PPC) with M_n = 9100 and M_w/M_n = 18. The productivity of this catalyst (5.6 g-PPC/(g-catalyst h)) is superior to the previous heterogeneous catalysts. From the time course, XRD and TEM measurement, needle-shaped CePO₄ can be the active phase. The reaction of CO₂ with 1,2-butylene oxide and cyclohexene oxide also gave the corresponding polycarbonates. Although the catalytic activity decreased in the reuse test, ICP analysis confirmed that the catalyst was removed from PPC by filtration under vacuum.

稀土磷酸盐是二氧化碳与环氧化物交替共聚的有效催化剂。这是首次报道在无溶剂条件下用完全无机非均相催化剂催化该反应。在各种稀土磷酸盐中，磷酸铈在CO2和环氧丙烷的反应中表现出最高的活性，得到了Mn = 9100,Mw/Mn = 18的聚碳酸丙烯（PPC）。该催化剂的产率（5.6 g-PPC/(g-catalyst h)）优于以往的多相催化剂。从时间过程、XRD和TEM测量结果来看，针状的CePO4可以是活性相。二氧化碳与1,2-环氧丁烯和环氧环己烯反应也得到了相应的聚碳酸酯。虽然在重复使用试验中催化活性下降，但ICP分析证实了催化剂在真空过滤下从PPC中去除。

引用次数: 0