Pub Date : 2025-12-11DOI: 10.1016/j.jcou.2025.103295
I-Jeong Jeon , Da-Bin Kang , Jae-Hak Lim , Ji-Hyeon Gong , Chang-Hyeon Kim , Min-Ju Kim , Min-Jun Kim , Kyung-Won Jeon , Ik Seon Kwon , Won-Jun Jang , Chang Hyun Ko , Jae-Oh Shim
The CO2 hydrogenation reaction is a promising route for mitigating greenhouse gas emissions by converting CO2 into value-added carbon monoxide through the reverse water–gas shift (RWGS) process. In this study, a surfactant-assisted mechanochemical synthesis was developed to prepare highly dispersed Cu catalysts supported on MgCeOx for the RWGS reaction. The combined use of CTAB (Hexadecyltrimethylammonium bromide, C19H42BrN) and Span®60 (Sorbitan monostearate, C24H46O6) enabled simultaneous control of Cu dispersion, oxygen vacancy concentration, and Ce3 + enrichment under solvent-minimized conditions. The optimized Cu@MgCeOx_CS catalyst achieved 25 % CO2 conversion and complete stability at 440 °C under a gas hourly space velocity (GHSV) of 50,000 h−1 with an H2/CO2 ratio of 4:1. Enhanced redox coupling between Cu+/Cu2 and Ce3+/Ce4+ was verified by precise X-ray analyses, confirming that Cu⁺ species act as the main active sites. This study demonstrates a scalable and energy-efficient route for the synthesis of uniformly mixed Cu–MgO–CeO2 catalysts and provides mechanistic insight into the relationship between surface redox properties and RWGS performance.
{"title":"Application of highly dispersed copper catalysts in CO2 hydrogenation through surfactant introduction","authors":"I-Jeong Jeon , Da-Bin Kang , Jae-Hak Lim , Ji-Hyeon Gong , Chang-Hyeon Kim , Min-Ju Kim , Min-Jun Kim , Kyung-Won Jeon , Ik Seon Kwon , Won-Jun Jang , Chang Hyun Ko , Jae-Oh Shim","doi":"10.1016/j.jcou.2025.103295","DOIUrl":"10.1016/j.jcou.2025.103295","url":null,"abstract":"<div><div>The CO<sub>2</sub> hydrogenation reaction is a promising route for mitigating greenhouse gas emissions by converting CO<sub>2</sub> into value-added carbon monoxide through the reverse water–gas shift (RWGS) process. In this study, a surfactant-assisted mechanochemical synthesis was developed to prepare highly dispersed Cu catalysts supported on MgCeO<sub>x</sub> for the RWGS reaction. The combined use of CTAB (Hexadecyltrimethylammonium bromide, C<sub>19</sub>H<sub>42</sub>BrN) and Span®60 (Sorbitan monostearate, C<sub>24</sub>H<sub>46</sub>O<sub>6</sub>) enabled simultaneous control of Cu dispersion, oxygen vacancy concentration, and Ce<sup>3 +</sup> enrichment under solvent-minimized conditions. The optimized Cu@MgCeO<sub>x</sub>_CS catalyst achieved 25 % CO<sub>2</sub> conversion and complete stability at 440 °C under a gas hourly space velocity (GHSV) of 50,000 h<sup>−1</sup> with an H<sub>2</sub>/CO<sub>2</sub> ratio of 4:1. Enhanced redox coupling between Cu<sup>+</sup>/Cu<sup>2</sup> and Ce<sup>3+</sup>/Ce<sup>4+</sup> was verified by precise X-ray analyses, confirming that Cu⁺ species act as the main active sites. This study demonstrates a scalable and energy-efficient route for the synthesis of uniformly mixed Cu–MgO–CeO<sub>2</sub> catalysts and provides mechanistic insight into the relationship between surface redox properties and RWGS performance.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103295"},"PeriodicalIF":8.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jcou.2025.103298
Ting Kong , Kefan Zhou , Jingnan Wang , Qiyi Zhao , Aizhen Liao , Xiaoshuang Qiao
Urea (NH₂CONH₂) plays a crucial role as both a nitrogen-based fertilizer and a key industrial raw material. Its conventional synthesis typically requires harsh conditions. In contrast, the electrocatalytic conversion of nitrogen (N₂) and carbon dioxide (CO₂) into urea has emerged as a promising alternative. However, achieving catalysts that offer both high activity and selectivity is still a huge challenge. This study utilizes density functional theory for investigating the electrochemical coupling between N₂ and CO₂ for the production of urea, specifically examining the performance of various transition metal clusters (from Groups IB and VIII) supported on C₂N catalysts. The results revealed that these catalysts demonstrate strong thermodynamic stability and effectively facilitate the co-adsorption of CO₂ and N₂. Notably, except Pd and Pt, most M₃/C₂N catalysts efficiently suppress the H2 evolution reaction, preventing the excessive protonation of CO and the generation of ammonia, thus guaranteeing high selectivity for urea. In particular, Ru₃ and Os₃/C₂N catalysts demonstrate lower free energies and promote C-N coupling via *N₂ and *CO intermediates. Further evaluation of the electronic structure of Os₃/C₂N revealed an "acceptance-donation" mechanism that enhanced the activation of *CO₂ and *N₂, with the Os₃ cluster playing a crucial role. This research provides a new approach for electrochemically synthesizing urea and offers valuable insights into the design of advanced electrocatalysts.
{"title":"Electrochemical production of urea using triatomic cluster/C2N catalysts: A DFT study","authors":"Ting Kong , Kefan Zhou , Jingnan Wang , Qiyi Zhao , Aizhen Liao , Xiaoshuang Qiao","doi":"10.1016/j.jcou.2025.103298","DOIUrl":"10.1016/j.jcou.2025.103298","url":null,"abstract":"<div><div>Urea (NH₂CONH₂) plays a crucial role as both a nitrogen-based fertilizer and a key industrial raw material. Its conventional synthesis typically requires harsh conditions. In contrast, the electrocatalytic conversion of nitrogen (N₂) and carbon dioxide (CO₂) into urea has emerged as a promising alternative. However, achieving catalysts that offer both high activity and selectivity is still a huge challenge. This study utilizes density functional theory for investigating the electrochemical coupling between N₂ and CO₂ for the production of urea, specifically examining the performance of various transition metal clusters (from Groups IB and VIII) supported on C₂N catalysts. The results revealed that these catalysts demonstrate strong thermodynamic stability and effectively facilitate the co-adsorption of CO₂ and N₂. Notably, except Pd and Pt, most M₃/C₂N catalysts efficiently suppress the H<sub>2</sub> evolution reaction, preventing the excessive protonation of CO and the generation of ammonia, thus guaranteeing high selectivity for urea. In particular, Ru₃ and Os₃/C₂N catalysts demonstrate lower free energies and promote C-N coupling via *N₂ and *CO intermediates. Further evaluation of the electronic structure of Os₃/C₂N revealed an \"acceptance-donation\" mechanism that enhanced the activation of *CO₂ and *N₂, with the Os₃ cluster playing a crucial role. This research provides a new approach for electrochemically synthesizing urea and offers valuable insights into the design of advanced electrocatalysts.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103298"},"PeriodicalIF":8.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jcou.2025.103294
Xinyang Li , Guilong Wang , Xiebin Wang , Guoqun Zhao
Microcellular foaming is one of the most promising method for preparing high-performance polymer foams. Gas diffusion and adsorption behavior can significantly affect the foaming behavior of polymers in microcellular foaming. However, it is still a challenging work to manipulate the gas diffusion and adsorption behavior for achieving desired performance of polymer foams. Herein, a novel pre-foaming strategy was proposed to manipulate carbon dioxide adsorption and desorption behavior for achieving low-density thermoplastic polyurethane (TPU) foams. It was demonstrated that pre-foaming is an efficient method for manipulating the diffusion and adsorption behavior of carbon dioxide in TPU matrix. Thanks to the newly created cellular structure by pre-foaming, both diffusion coefficient and adsorption amount increase gradually with increasing the pre-foamed expansion ratio of TPU. For the pre-foamed expansion ratio of 2.0, the gas solubility was increased by 92.8 %, the diffusion coefficients in adsorption and desorption were increased by 54.0 % and 111.0 %, respectively. Interestingly, pre-foaming can lead to a more perfect crystal structure, while destroying the hydrogen bond structure of TPU chains. Owing to the significantly increased gas adsorption capacity and greatly reduced cell growth resistance, the pre-foaming strategy can lead to remarkably increased expansion ratio of the TPU foams. All the TPU foams prepared without pre-foaming have a maximum expansion ratio less than 4, while those prepared with pre-foaming can have an expansion ratio larger than 16. This new microcellular foaming technique with pre-foaming provides a novel approach for preparing low-density thermoplastic elastomer foams.
{"title":"A novel pre-foaming strategy to manipulate carbon dioxide adsorption and desorption behavior for achieving low-density TPU foams","authors":"Xinyang Li , Guilong Wang , Xiebin Wang , Guoqun Zhao","doi":"10.1016/j.jcou.2025.103294","DOIUrl":"10.1016/j.jcou.2025.103294","url":null,"abstract":"<div><div>Microcellular foaming is one of the most promising method for preparing high-performance polymer foams. Gas diffusion and adsorption behavior can significantly affect the foaming behavior of polymers in microcellular foaming. However, it is still a challenging work to manipulate the gas diffusion and adsorption behavior for achieving desired performance of polymer foams. Herein, a novel pre-foaming strategy was proposed to manipulate carbon dioxide adsorption and desorption behavior for achieving low-density thermoplastic polyurethane (TPU) foams. It was demonstrated that pre-foaming is an efficient method for manipulating the diffusion and adsorption behavior of carbon dioxide in TPU matrix. Thanks to the newly created cellular structure by pre-foaming, both diffusion coefficient and adsorption amount increase gradually with increasing the pre-foamed expansion ratio of TPU. For the pre-foamed expansion ratio of 2.0, the gas solubility was increased by 92.8 %, the diffusion coefficients in adsorption and desorption were increased by 54.0 % and 111.0 %, respectively. Interestingly, pre-foaming can lead to a more perfect crystal structure, while destroying the hydrogen bond structure of TPU chains. Owing to the significantly increased gas adsorption capacity and greatly reduced cell growth resistance, the pre-foaming strategy can lead to remarkably increased expansion ratio of the TPU foams. All the TPU foams prepared without pre-foaming have a maximum expansion ratio less than 4, while those prepared with pre-foaming can have an expansion ratio larger than 16. This new microcellular foaming technique with pre-foaming provides a novel approach for preparing low-density thermoplastic elastomer foams.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103294"},"PeriodicalIF":8.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jcou.2025.103297
Ji Hyeon Whang , Yooseob Won , A Ra Cho , Yunji Son , Yongseon Lee , Yuntae Hwang , Dong-Kyu Moon , Jae-Young Kim , Sung-Ho Jo , Young Cheol Park , Ki Bong Lee , Dong-Ho Lee
Carbon capture utilization and storage (CCUS) is a crucial strategy to mitigate climate change, with solid sorbents are promising option due to their energy efficiency. A macroporous silica (MPS) adsorbent functionalized with propylene oxide (PO)-modified pentaethylenehexamine (PEHA) (2.0PO-PEHA/MPS) showed effective CO2 capture from both coal-fired power plant (CFPP) and natural gas combined cycle (NGCC) flue gases, as confirmed by CO2 isotherm measurements. Building on our previous work with CFPP flue gas, this study investigates its performance under NGCC conditions using the programmed adsorption–desorption (TPAD) method with a stainless-steel fixed-bed reactor. The optimal conditions were identified as 50 ℃ for adsorption and 120 ℃ for regeneration. Cyclic adsorption–regeneration experiments performed by thermogravimetric analysis (TGA) showed stable working capacity over 20 cycles. Notably, TGA tended to overestimate H2O uptake because it did not fully account for the competitive adsorption between CO2 and H2O. To overcome this limitation, Our TPAD method, a more process-relevant fixed-bed flow approach, was introduced, providing highly reliable and quantitative results (CO2: 10.28 wt%, H2O: 3.51 wt%). Based on TPAD data, the theoretical regeneration heat was calculated to be 2.96–79 GJ tCO2−1 at 120 ℃, representing a relatively low value compared with other materials. These results highlight the potential of 2.0PO-PEHA/MPS for CO2 capture from NGCC flue gas, underscore the critical role of TPAD-based quantification for accurately determining low regeneration heat, thereby advancing the field of CO2 capture.
{"title":"Highly efficient silica adsorbent functionalized with propylene oxide-modified pentaethylenehexamine for CO2 capture under NGCC flue gas conditions","authors":"Ji Hyeon Whang , Yooseob Won , A Ra Cho , Yunji Son , Yongseon Lee , Yuntae Hwang , Dong-Kyu Moon , Jae-Young Kim , Sung-Ho Jo , Young Cheol Park , Ki Bong Lee , Dong-Ho Lee","doi":"10.1016/j.jcou.2025.103297","DOIUrl":"10.1016/j.jcou.2025.103297","url":null,"abstract":"<div><div>Carbon capture utilization and storage (CCUS) is a crucial strategy to mitigate climate change, with solid sorbents are promising option due to their energy efficiency. A macroporous silica (MPS) adsorbent functionalized with propylene oxide (PO)-modified pentaethylenehexamine (PEHA) (2.0PO-PEHA/MPS) showed effective CO<sub>2</sub> capture from both coal-fired power plant (CFPP) and natural gas combined cycle (NGCC) flue gases, as confirmed by CO<sub>2</sub> isotherm measurements. Building on our previous work with CFPP flue gas, this study investigates its performance under NGCC conditions using the programmed adsorption–desorption (TPAD) method with a stainless-steel fixed-bed reactor. The optimal conditions were identified as 50 ℃ for adsorption and 120 ℃ for regeneration. Cyclic adsorption–regeneration experiments performed by thermogravimetric analysis (TGA) showed stable working capacity over 20 cycles. Notably, TGA tended to overestimate H<sub>2</sub>O uptake because it did not fully account for the competitive adsorption between CO<sub>2</sub> and H<sub>2</sub>O. To overcome this limitation, Our TPAD method, a more process-relevant fixed-bed flow approach, was introduced, providing highly reliable and quantitative results (CO<sub>2</sub>: 10.28 wt%, H<sub>2</sub>O: 3.51 wt%). Based on TPAD data, the theoretical regeneration heat was calculated to be 2.96–79 GJ tCO<sub>2</sub><sup>−1</sup> at 120 ℃, representing a relatively low value compared with other materials. These results highlight the potential of 2.0PO-PEHA/MPS for CO<sub>2</sub> capture from NGCC flue gas, underscore the critical role of TPAD-based quantification for accurately determining low regeneration heat, thereby advancing the field of CO<sub>2</sub> capture.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103297"},"PeriodicalIF":8.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jcou.2025.103284
Meng Ding , Yuqi Ji , Du Yanchen
The continuous rise in atmospheric carbon dioxide (CO₂) levels, primarily driven by extensive petroleum energy consumption, is a major contributor to global climate change. A promising approach to mitigate this issue is Carbon Capture, Utilization, and Storage (CCUS), where CO₂ capture plays a pivotal role. Among emerging biological solutions, carbonic anhydrase—a natural enzyme that catalyzes the conversion of CO₂ into bicarbonate—has gained considerable attention for its potential in efficient carbon capture. Despite its promise, large-scale industrial application faces challenges due to the enzyme’s instability, volatility, and high production costs. To address these limitations, three key strategies have been developed: enzyme engineering to improve performance, immobilization techniques to enhance stability and reusability, and the development of synthetic analogs known as carbonic anhydrase mimics. These approaches not only improve the enzyme's resilience but also expand its applicability in harsh industrial conditions. Additionally, studies are focusing on optimizing the interaction between support materials and the enzyme to boost catalytic efficiency. The development of enzyme mimics, particularly through improved metal-ligand coordination, offers a cost-effective and stable alternative. Collectively, these innovations represent a significant step toward sustainable carbon management, providing scalable and environmentally friendly solutions for reducing greenhouse gas emissions.
{"title":"Accelerating sustainable development in hard-to-abate sectors: An economic case for enzymatic carbon capture","authors":"Meng Ding , Yuqi Ji , Du Yanchen","doi":"10.1016/j.jcou.2025.103284","DOIUrl":"10.1016/j.jcou.2025.103284","url":null,"abstract":"<div><div>The continuous rise in atmospheric carbon dioxide (CO₂) levels, primarily driven by extensive petroleum energy consumption, is a major contributor to global climate change. A promising approach to mitigate this issue is Carbon Capture, Utilization, and Storage (CCUS), where CO₂ capture plays a pivotal role. Among emerging biological solutions, carbonic anhydrase—a natural enzyme that catalyzes the conversion of CO₂ into bicarbonate—has gained considerable attention for its potential in efficient carbon capture. Despite its promise, large-scale industrial application faces challenges due to the enzyme’s instability, volatility, and high production costs. To address these limitations, three key strategies have been developed: enzyme engineering to improve performance, immobilization techniques to enhance stability and reusability, and the development of synthetic analogs known as carbonic anhydrase mimics. These approaches not only improve the enzyme's resilience but also expand its applicability in harsh industrial conditions. Additionally, studies are focusing on optimizing the interaction between support materials and the enzyme to boost catalytic efficiency. The development of enzyme mimics, particularly through improved metal-ligand coordination, offers a cost-effective and stable alternative. Collectively, these innovations represent a significant step toward sustainable carbon management, providing scalable and environmentally friendly solutions for reducing greenhouse gas emissions.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103284"},"PeriodicalIF":8.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-08DOI: 10.1016/j.jcou.2025.103292
Yuanzhu Long , Yuanzhe Yan , Hairong Yue , Xingyi Xie
Among organic amines, polyethylenimines (PEIs) have been widely utilized to functionalize various porous solid sorbents to capture CO2, aiming to mitigate global warming. However, low CO2 capacity (due to limited CO2 diffusion) and CO2-induced amine degradation hinder their commercialization. In this study, we developed a series of alkyl (C4 to C12) grafted PEIs. The optimized specimen, 1:9-C12-25kPEI, in which 1 in 9 amine groups are alkylated with C12 alkyl chains (PEI backbone Mn = 25k Da), demonstrated much higher CO2 capacity (180 mg CO2 per 1 g PEI) compared with the control specimen 25kPEI (10 mg CO2 per 1 g PEI) at ambient temperature and pressure (14 °C and 100 % CO2), with a 0.21-mm thick liquid specimen layer. The corresponding half capacity times (t0.5) of the specimens were 8.8 and 43.7 s, respectively. The improved capture kinetics is due to the formation of a microphase separation structure in the alkylated PEI, where the continuous alkyl-dominated phase facilitates CO2 diffusion into the bulk (about 70 μm in depth) to access amine groups in PEI-dominated nanodots (about 13 nm in diameter). Moreover, the rapid CO2 capture consumes free amine groups quickly, avoiding CO2-induced amine degradation in consecutive absorption-desorption cycles at 65 and 95 °C. The alkylated PEIs possess a strong capability to capture CO2, insensitive to capture temperature (14–65 °C) and the mesoporous structure of solid supports. They are suitable for capturing CO2 across a wide temperature range and at various CO2 partial pressures (from air to post-combustion flue gases).
在有机胺中，聚乙烯胺（PEIs）被广泛用于功能化各种多孔固体吸附剂来捕获二氧化碳，旨在减缓全球变暖。然而，低CO2容量（由于CO2扩散有限）和CO2诱导的胺降解阻碍了它们的商业化。在这项研究中，我们开发了一系列烷基（C4至C12）接枝的pei。优化后的样品为1:9-C12-25kPEI，其中9个胺基中有1个与C12烷基链烷基化（PEI主链Mn = 25k Da），在环境温度和压力下（14°C和100 % CO2），具有0.21 mm厚的液体样品层，与对照样品25kPEI（10 mg CO2 / 1 g PEI）相比，其CO2容量（180 mg CO2 / 1 g PEI）要高得多。试件相应的半容量倍（t0.5）分别为8.8和43.7 s。捕获动力学的改善是由于在烷基化的PEI中形成了微相分离结构，其中连续的烷基主导相促进了CO2扩散到主体（约70 μm深度）中，以接近PEI主导的纳米点（直径约13 nm）中的胺基。此外，快速CO2捕获可以快速消耗游离胺基，避免在65°C和95°C的连续吸收-解吸循环中二氧化碳诱导的胺降解。烷基化PEIs具有较强的CO2捕集能力，对捕集温度（14 ~ 65℃）和固体载体的介孔结构不敏感。它们适用于在很宽的温度范围和各种CO2分压（从空气到燃烧后烟气）下捕获CO2。
{"title":"Enhanced CO2 capture rate and capacity through alkylation of polyethylenimines forming a microphase separation structure","authors":"Yuanzhu Long , Yuanzhe Yan , Hairong Yue , Xingyi Xie","doi":"10.1016/j.jcou.2025.103292","DOIUrl":"10.1016/j.jcou.2025.103292","url":null,"abstract":"<div><div>Among organic amines, polyethylenimines (PEIs) have been widely utilized to functionalize various porous solid sorbents to capture CO<sub>2</sub>, aiming to mitigate global warming. However, low CO<sub>2</sub> capacity (due to limited CO<sub>2</sub> diffusion) and CO<sub>2</sub>-induced amine degradation hinder their commercialization. In this study, we developed a series of alkyl (C<sub>4</sub> to C<sub>12</sub>) grafted PEIs. The optimized specimen, 1:9-C<sub>12</sub>-25kPEI, in which 1 in 9 amine groups are alkylated with C<sub>12</sub> alkyl chains (PEI backbone <em>M</em><sub>n</sub> = 25k Da), demonstrated much higher CO<sub>2</sub> capacity (180 mg CO<sub>2</sub> per 1 g PEI) compared with the control specimen 25kPEI (10 mg CO<sub>2</sub> per 1 g PEI) at ambient temperature and pressure (14 °C and 100 % CO<sub>2</sub>), with a 0.21-mm thick liquid specimen layer. The corresponding half capacity times (<em>t</em><sub>0.5</sub>) of the specimens were 8.8 and 43.7 s, respectively. The improved capture kinetics is due to the formation of a microphase separation structure in the alkylated PEI, where the continuous alkyl-dominated phase facilitates CO<sub>2</sub> diffusion into the bulk (about 70 μm in depth) to access amine groups in PEI-dominated nanodots (about 13 nm in diameter). Moreover, the rapid CO<sub>2</sub> capture consumes free amine groups quickly, avoiding CO<sub>2</sub>-induced amine degradation in consecutive absorption-desorption cycles at 65 and 95 °C. The alkylated PEIs possess a strong capability to capture CO<sub>2</sub>, insensitive to capture temperature (14–65 °C) and the mesoporous structure of solid supports. They are suitable for capturing CO<sub>2</sub> across a wide temperature range and at various CO<sub>2</sub> partial pressures (from air to post-combustion flue gases).</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103292"},"PeriodicalIF":8.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liquefied petroleum gas (LPG), primarily composed of propane and butane, is a versatile, clean-burning fuel with lower CO2 emissions compared to coal and oil. Conventionally produced as a byproduct of natural gas processing and crude oil refining, LPG faces sustainability challenges due to its dependency on fossil fuels. Recent advances in heterogeneous catalysis offer alternative pathways for LPG synthesis from syngas and CO2 hydrogenation, presenting opportunities to diversify feedstocks and mitigate greenhouse gas emissions. This review critically examines both the direct route, involving a single-stage reactor, and the indirect route, using a two-stage reactor, for LPG production, with an emphasis on hybrid catalysts that couple methanol synthesis-active phases with acidic zeolites to enable sequential conversion. Particular attention is given to various metal-based catalysts, including Cu, Pd, In, Fe, and Zn, as well as catalyst design strategies such as core-shell structures, promoter incorporation, and zeolite modifications. The impact of operating parameters on activity, selectivity, and stability is also examined. A comparative analysis highlights the advantages of direct, one-step processes in terms of energy efficiency and scalability, while indirect, multi-step routes offer greater control over product distribution. Finally, the review outlines key challenges, including catalyst deactivation, water tolerance, and process integration, and discusses future directions toward sustainable, high-selectivity LPG production from renewable carbon resources.
{"title":"Recent advancements in thermocatalytic hydrogenation of syngas and carbon dioxide into LPG through heterogeneous catalysis","authors":"Haripal Singh Malhi , Bantayehu Uba Uge , Lenka Matějová","doi":"10.1016/j.jcou.2025.103290","DOIUrl":"10.1016/j.jcou.2025.103290","url":null,"abstract":"<div><div>Liquefied petroleum gas (LPG), primarily composed of propane and butane, is a versatile, clean-burning fuel with lower CO<sub>2</sub> emissions compared to coal and oil. Conventionally produced as a byproduct of natural gas processing and crude oil refining, LPG faces sustainability challenges due to its dependency on fossil fuels. Recent advances in heterogeneous catalysis offer alternative pathways for LPG synthesis from syngas and CO<sub>2</sub> hydrogenation, presenting opportunities to diversify feedstocks and mitigate greenhouse gas emissions. This review critically examines both the direct route, involving a single-stage reactor, and the indirect route, using a two-stage reactor, for LPG production, with an emphasis on hybrid catalysts that couple methanol synthesis-active phases with acidic zeolites to enable sequential conversion. Particular attention is given to various metal-based catalysts, including Cu, Pd, In, Fe, and Zn, as well as catalyst design strategies such as core-shell structures, promoter incorporation, and zeolite modifications. The impact of operating parameters on activity, selectivity, and stability is also examined. A comparative analysis highlights the advantages of direct, one-step processes in terms of energy efficiency and scalability, while indirect, multi-step routes offer greater control over product distribution. Finally, the review outlines key challenges, including catalyst deactivation, water tolerance, and process integration, and discusses future directions toward sustainable, high-selectivity LPG production from renewable carbon resources.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103290"},"PeriodicalIF":8.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.jcou.2025.103281
Lotfi Ben Said , Ramadan Youssef Sakr , Loghman Mostafa , Mehraj-ud-din Naik , Mohamed Shaban , Abdellatif M. Sadeq , Wajdi Rajhi , Khalil Hajlaoui
A hybrid biomass-fired polygeneration plant integrating a gas turbine, a supercritical CO2 Brayton loop, and an alkaline electrolyzer was developed to co-produce hydrogen, oxygen, electricity, and process heat. Rice Husk (RH) and Corn Stover (CS) feedstocks were assessed under identical thermodynamic boundaries to examine energy efficiency and carbon performance. The model, formulated in MATLAB, combined detailed mass- and energy-balance equations with an extended heat-recovery network. Multi-objective optimization using NSGA-II aimed to maximize hydrogen generation, limit CO2 emissions, and raise overall efficiency. Parametric analysis revealed that higher turbine pressure ratios strengthen electrical output and diminish carbon intensity, whereas elevated turbine‑inlet temperatures promote thermal energy recovery but slightly lower global efficiency. Pareto‑optimal configurations displayed clear trade-offs between feedstocks: the RH case (PR = 18, Tg = 950 K) yielded 2.45 kg h−1 of H2, 37 kg h−1 of CO2, and 42.2 % efficiency; the CS counterpart produced 3.05 kg h−1 of H2 and 45 kg h−1 of CO2 at 40.5 % efficiency. The cascade turbine coupling and electrolysis pre-heating loop ensure full use of available thermal exergy and confirm strong thermodynamic synergy across both fuels. Sensitivity testing on PR, Tg, and BFR demonstrated model stability with deviations below 3 %. Overall, the findings establish a reproducible and feedstock-adaptive framework for high-efficiency, low-carbon, multi-output biomass energy systems suited to decentralized power and hydrogen production.
开发了一种混合生物质燃烧多联产装置，集成了燃气轮机、超临界二氧化碳布雷顿循环和碱性电解槽，以共同生产氢、氧、电和加工热。在相同的热力学边界下对稻壳（RH）和玉米秸秆（CS）原料进行了评估，以考察其能源效率和碳性能。该模型在MATLAB中建立，将详细的质量和能量平衡方程与扩展的热回收网络相结合。利用NSGA-II进行多目标优化，旨在最大限度地产生氢气，限制二氧化碳排放，提高整体效率。参数分析表明，较高的涡轮压力比可以增强电力输出并降低碳强度，而涡轮进口温度升高可以促进热能回收，但会略微降低整体效率。帕累托最优配置显示了原料之间的明确权衡：RH情况（PR = 18, Tg = 950 K）产生2.45 kg h−1 H2, 37 kg h−1 CO2，效率为42.2% %；对应的CS以40.5% %的效率产生3.05 kg h−1的H2和45 kg h−1的CO2。级联涡轮耦合和电解预热回路确保充分利用可用的热用能，并确认两种燃料之间强大的热力学协同作用。PR、Tg和BFR的敏感性测试表明，模型的稳定性偏差小于3 %。总的来说，研究结果为高效、低碳、多输出的生物质能源系统建立了一个可复制的、适应原料的框架，适合分散的电力和氢气生产。
{"title":"Multi-objective optimization of a biomass-fired supercritical CO2 Brayton–electrolysis system for high‑efficiency hydrogen, power, and cogenerative thermal services","authors":"Lotfi Ben Said , Ramadan Youssef Sakr , Loghman Mostafa , Mehraj-ud-din Naik , Mohamed Shaban , Abdellatif M. Sadeq , Wajdi Rajhi , Khalil Hajlaoui","doi":"10.1016/j.jcou.2025.103281","DOIUrl":"10.1016/j.jcou.2025.103281","url":null,"abstract":"<div><div>A hybrid biomass-fired polygeneration plant integrating a gas turbine, a supercritical CO<sub>2</sub> Brayton loop, and an alkaline electrolyzer was developed to co-produce hydrogen, oxygen, electricity, and process heat. Rice Husk (RH) and Corn Stover (CS) feedstocks were assessed under identical thermodynamic boundaries to examine energy efficiency and carbon performance. The model, formulated in MATLAB, combined detailed mass- and energy-balance equations with an extended heat-recovery network. Multi-objective optimization using NSGA-II aimed to maximize hydrogen generation, limit CO<sub>2</sub> emissions, and raise overall efficiency. Parametric analysis revealed that higher turbine pressure ratios strengthen electrical output and diminish carbon intensity, whereas elevated turbine‑inlet temperatures promote thermal energy recovery but slightly lower global efficiency. Pareto‑optimal configurations displayed clear trade-offs between feedstocks: the RH case (PR = 18, Tg = 950 K) yielded 2.45 kg h<sup>−1</sup> of H<sub>2</sub>, 37 kg h<sup>−1</sup> of CO<sub>2</sub>, and 42.2 % efficiency; the CS counterpart produced 3.05 kg h<sup>−1</sup> of H<sub>2</sub> and 45 kg h<sup>−1</sup> of CO<sub>2</sub> at 40.5 % efficiency. The cascade turbine coupling and electrolysis pre-heating loop ensure full use of available thermal exergy and confirm strong thermodynamic synergy across both fuels. Sensitivity testing on PR, Tg, and BFR demonstrated model stability with deviations below 3 %. Overall, the findings establish a reproducible and feedstock-adaptive framework for high-efficiency, low-carbon, multi-output biomass energy systems suited to decentralized power and hydrogen production.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103281"},"PeriodicalIF":8.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692797","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.jcou.2025.103289
Xuewen Cao , Jiao Zhou , Chaoqi Qiu , Hao Li , Lvruoxi Zhao , Jiang Bian
This study systematically investigates the dissolution behavior and regulatory mechanisms of carbon dioxide (CO₂) in oil-water mixtures through a multiscale approach integrating experiments and molecular dynamics (MD) simulations. Experimental results demonstrate that CO₂ solubility exhibits significant pressure-increasing and temperature-decreasing trends, reaching a peak value of 1.422 mol·L⁻¹ at an oil-to-water ratio of 2:1 (5.2 MPa), which is 37 % higher than the 1:2 ratio. CO₂ solubility in crude oil is 2–3 times higher than in the aqueous phase. MD simulations reveal the enrichment effect of CO₂ at oil-water interfaces (density 1.9 times higher than the bulk phase) and the mass transfer mechanism dominated by interfacial tension reduction (γ decreases from 57.9 to 46.2 mN·m⁻¹). Based on experimental data, the Taylor model (for the oil phase, MRE (Mean relative error) = 1.75 %) and Duan model (for the aqueous phase, MRE = 2.17 %) were optimized. A composite predictive model for oil-water mixtures was developed, achieving an overall MRE of 3.54 %, significantly outperforming traditional models (error reduction by 85 %). This research provides a high-precision theoretical framework for CO₂-enhanced oil recovery (EOR) and carbon sequestration, elucidating the critical role of multiphase interfacial behavior in dissolution kinetics.
{"title":"Multiscale investigation of CO₂ solubility behavior in oil-water mixtures: Experiments, molecular dynamics simulations, and predictive model optimization","authors":"Xuewen Cao , Jiao Zhou , Chaoqi Qiu , Hao Li , Lvruoxi Zhao , Jiang Bian","doi":"10.1016/j.jcou.2025.103289","DOIUrl":"10.1016/j.jcou.2025.103289","url":null,"abstract":"<div><div>This study systematically investigates the dissolution behavior and regulatory mechanisms of carbon dioxide (CO₂) in oil-water mixtures through a multiscale approach integrating experiments and molecular dynamics (MD) simulations. Experimental results demonstrate that CO₂ solubility exhibits significant pressure-increasing and temperature-decreasing trends, reaching a peak value of 1.422 mol·L⁻¹ at an oil-to-water ratio of 2:1 (5.2 MPa), which is 37 % higher than the 1:2 ratio. CO₂ solubility in crude oil is 2–3 times higher than in the aqueous phase. MD simulations reveal the enrichment effect of CO₂ at oil-water interfaces (density 1.9 times higher than the bulk phase) and the mass transfer mechanism dominated by interfacial tension reduction (<em>γ</em> decreases from 57.9 to 46.2 mN·m⁻¹). Based on experimental data, the Taylor model (for the oil phase, MRE (Mean relative error) = 1.75 %) and Duan model (for the aqueous phase, MRE = 2.17 %) were optimized. A composite predictive model for oil-water mixtures was developed, achieving an overall MRE of 3.54 %, significantly outperforming traditional models (error reduction by 85 %). This research provides a high-precision theoretical framework for CO₂-enhanced oil recovery (EOR) and carbon sequestration, elucidating the critical role of multiphase interfacial behavior in dissolution kinetics.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103289"},"PeriodicalIF":8.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-05DOI: 10.1016/j.jcou.2025.103291
Tao Chen , Ying Zhang , Lingbo Dang , Fang Jin , Meng Song , Qin Liu , Xiang Zhu , Zhong Han
Carbonation treatment can improve the hydration reactivity of steel slag powders. However, the reaction rate and degree of CaCO3 contained in carbonated steel slag powders were usually low, which cannot fully exert its hydration reactivity. This paper utilized a synergistic strategy of CO2 mineralization and aluminate activation to fully stimulate the hydration reactivity of ladle furnace slag (LFS), and prepared highly reactive powders (HRPs). There was a significant synergistic hydration effect between carbonated LFS and MK. CaCO3 in carbonated LFS and the active aluminum phase in MK could generate monocarbonate in the early - age hydration, while consuming Ca(OH)2, which greatly refined the pores of cement-based materials and improved the interface structure between steel slag particles and matrix. At the age of 3 day, the compressive strength of cement mortar mixed with carbonated LFS was 2.1 MPa higher than that mixed with LFS. The addition of MK could increase this effect to 7.7 MPa. When the dosage reached 40 wt%, the compressive strength of composite cement at 3 day, 7 day, and 28 day was much higher than that of pure cement mortar. This article provides theoretical and technical support for exploring the characteristics and reaction mechanisms of Ca - containing alkaline solid waste and aluminum - rich solid waste, optimizing carbonation processes and composite schemes, and achieving sustainable development and carbon neutrality.
{"title":"Utilizing CO2 mineralization and aluminate synergistic activation of metallurgical solid waste to produce highly reactive powders: Toward sustainable engineering materials","authors":"Tao Chen , Ying Zhang , Lingbo Dang , Fang Jin , Meng Song , Qin Liu , Xiang Zhu , Zhong Han","doi":"10.1016/j.jcou.2025.103291","DOIUrl":"10.1016/j.jcou.2025.103291","url":null,"abstract":"<div><div>Carbonation treatment can improve the hydration reactivity of steel slag powders. However, the reaction rate and degree of CaCO<sub>3</sub> contained in carbonated steel slag powders were usually low, which cannot fully exert its hydration reactivity. This paper utilized a synergistic strategy of CO<sub>2</sub> mineralization and aluminate activation to fully stimulate the hydration reactivity of ladle furnace slag (LFS), and prepared highly reactive powders (HRPs). There was a significant synergistic hydration effect between carbonated LFS and MK. CaCO<sub>3</sub> in carbonated LFS and the active aluminum phase in MK could generate monocarbonate in the early - age hydration, while consuming Ca(OH)<sub>2</sub>, which greatly refined the pores of cement-based materials and improved the interface structure between steel slag particles and matrix. At the age of 3 day, the compressive strength of cement mortar mixed with carbonated LFS was 2.1 MPa higher than that mixed with LFS. The addition of MK could increase this effect to 7.7 MPa. When the dosage reached 40 wt%, the compressive strength of composite cement at 3 day, 7 day, and 28 day was much higher than that of pure cement mortar. This article provides theoretical and technical support for exploring the characteristics and reaction mechanisms of Ca - containing alkaline solid waste and aluminum - rich solid waste, optimizing carbonation processes and composite schemes, and achieving sustainable development and carbon neutrality.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"103 ","pages":"Article 103291"},"PeriodicalIF":8.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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