Pub Date : 2025-10-28DOI: 10.1016/j.jcou.2025.103260
Ai-zhen Liao , Qing-hua Xie , Lin-ji Zhang , Wei Ren , Yong Wang , Chao Yang , Xiao-hong Jiang , Yong Zhou , Zhi-gang Zou
A robust S-O covalent-bonded In2S3/α-Fe2O3 nanorod arrays heterojunction were successfully synthesized via a modified heat treatment strategy. The resulting photoanode exhibits an exceptional photocurrent density of 2.65 mA cm−2 at 1.23 V vs. RHE, achieving a 235 % enhancement compared to robust bare α-Fe2O3 (1.13 mA cm−2 at 1.23 V vs. RHE). To our knowledge, this represents the highest photocurrent density among all reported In2S3/α-Fe2O3 systems. Moreover, the photoanode demonstrates excellent stability, maintaining over 95 % of its initial performance over 3 h in alkaline electrolyte. The outstanding PEC performances of robust S-O bonded In2S3/α-Fe2O3 photoanode originates from a synergistic effect of the following aspects: (i) Locking the morphology of FeOOH nanorod array precursor through the improved thermal annealing method decreases charge-carrier recombination; (ⅰi) Forming atomic-level S-O covalent bonds provide direct charge-transfer pathways, thereby enhancing carrier lifetime and reducing interfacial resistance; (iii) Constructing a type-II heterojunction establishes a strong internal electric field that provides a large driving force for the rapid migration of photogenerated charges; and (iv) Loading In2S3 efficiently passivates surface defects and promotes hole injection.
通过改进热处理策略，成功合成了一种坚固的S-O共价键In2S3/α-Fe2O3纳米棒阵列异质结。所得到的光阳极在1.23 V vs. RHE下具有2.65 mA cm−2的特殊光电流密度，与α-Fe2O3裸阳极（1.13 mA cm−2,1.23 V vs. RHE）相比，增强了235 %。据我们所知，这代表了所有报道的In2S3/α-Fe2O3体系中最高的光电流密度。此外，光阳极表现出优异的稳定性，在碱性电解质中3 h内保持95% %以上的初始性能。S-O键合In2S3/α-Fe2O3光阳极的优异PEC性能源于以下几个方面的协同效应：(1)通过改进的热退火方法锁定FeOOH纳米棒阵列前驱体的形貌，减少电荷载流子复合；（ⅰ）形成原子级S-O共价键提供了直接的电荷转移途径，从而提高了载流子寿命，降低了界面阻力；（iii）构建ii型异质结建立了强大的内部电场，为光生电荷的快速迁移提供了巨大的驱动力；(4)加载In2S3能有效钝化表面缺陷，促进孔内注入。
{"title":"Synthesis of robust S-O covalent-bonded In2S3/α-Fe2O3 nanorod arrays heterojunction with a tailored heat treatment strategy for enhanced photoelectrochemical water splitting","authors":"Ai-zhen Liao , Qing-hua Xie , Lin-ji Zhang , Wei Ren , Yong Wang , Chao Yang , Xiao-hong Jiang , Yong Zhou , Zhi-gang Zou","doi":"10.1016/j.jcou.2025.103260","DOIUrl":"10.1016/j.jcou.2025.103260","url":null,"abstract":"<div><div>A robust S-O covalent-bonded In<sub>2</sub>S<sub>3</sub>/α-Fe<sub>2</sub>O<sub>3</sub> nanorod arrays heterojunction were successfully synthesized via a modified heat treatment strategy. The resulting photoanode exhibits an exceptional photocurrent density of 2.65 mA cm<sup>−2</sup> at 1.23 V vs. RHE, achieving a 235 % enhancement compared to robust bare α-Fe<sub>2</sub>O<sub>3</sub> (1.13 mA cm<sup>−2</sup> at 1.23 V vs. RHE). To our knowledge, this represents the highest photocurrent density among all reported In<sub>2</sub>S<sub>3</sub>/α-Fe<sub>2</sub>O<sub>3</sub> systems. Moreover, the photoanode demonstrates excellent stability, maintaining over 95 % of its initial performance over 3 h in alkaline electrolyte. The outstanding PEC performances of robust S-O bonded In<sub>2</sub>S<sub>3</sub>/α-Fe<sub>2</sub>O<sub>3</sub> photoanode originates from a synergistic effect of the following aspects: (i) Locking the morphology of FeOOH nanorod array precursor through the improved thermal annealing method decreases charge-carrier recombination; (ⅰi) Forming atomic-level S-O covalent bonds provide direct charge-transfer pathways, thereby enhancing carrier lifetime and reducing interfacial resistance; (iii) Constructing a type-II heterojunction establishes a strong internal electric field that provides a large driving force for the rapid migration of photogenerated charges; and (iv) Loading In<sub>2</sub>S<sub>3</sub> efficiently passivates surface defects and promotes hole injection.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103260"},"PeriodicalIF":8.4,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412412","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 : 2025-10-28DOI: 10.1016/j.jcou.2025.103263
Wenjing Guo , Yannan Zhou , Binbin Hu , Kanglin Feng , Xuefeng Wei , Shouren Zhang , Baocheng Yang
Conventional hydrophobic ceramic coatings exhibit compromised mechanochemical robustness due to static templating and decoupled organic-inorganic assembly. Here we introduce a supercritical carbon dioxide (SC CO2) strategy to engineer mesoscale self-assembly—where interactive inorganic-organic building blocks couple across time and space—to enable hierarchical structured hydroxyapatite (HAP) nanofiber bundles with embedded hydrophobicity. Our findings demonstrate that SC CO2 generates dynamic microcompartments and a mildly acidic environment that not only facilitate the rapid growth of HAP nanofibers with restricted c-axis orientation but also establish directional Ca2 + –PO43− ionic bridges that interconnect nanofibers into a cohesive inorganic network, in which oleate anions (OL−) in situ bind at ionic junctions via bidentate chelation, forming a robust hydrophobic layer. This green and scalable process yields advanced hydrophobic ceramic coatings, which have been successfully used to construct HAP-based fire-resistant paper with superior self-cleaning and oil-water separation capability, as well as sustainable Chinese Xuan paper with enhanced writing performance. Such mesoscale engineering, which unifies synthesis, assembly, and function, represents a new paradigm for creating robust, multifunctional biomimetic materials.
{"title":"Ion-bridged hydroxyapatite nanofiber bundles via supercritical CO2-mediated mesoscale nanoarchitectonic for robust hydrophobicity","authors":"Wenjing Guo , Yannan Zhou , Binbin Hu , Kanglin Feng , Xuefeng Wei , Shouren Zhang , Baocheng Yang","doi":"10.1016/j.jcou.2025.103263","DOIUrl":"10.1016/j.jcou.2025.103263","url":null,"abstract":"<div><div>Conventional hydrophobic ceramic coatings exhibit compromised mechanochemical robustness due to static templating and decoupled organic-inorganic assembly. Here we introduce a supercritical carbon dioxide (SC CO<sub>2</sub>) strategy to engineer mesoscale self-assembly—where interactive inorganic-organic building blocks couple across time and space—to enable hierarchical structured hydroxyapatite (HAP) nanofiber bundles with embedded hydrophobicity. Our findings demonstrate that SC CO<sub>2</sub> generates dynamic microcompartments and a mildly acidic environment that not only facilitate the rapid growth of HAP nanofibers with restricted <em>c</em>-axis orientation but also establish directional Ca<sup>2 +</sup> –PO<sub>4</sub><sup>3−</sup> ionic bridges that interconnect nanofibers into a cohesive inorganic network, in which oleate anions (OL<sup>−</sup>) <em>in situ</em> bind at ionic junctions via bidentate chelation, forming a robust hydrophobic layer. This green and scalable process yields advanced hydrophobic ceramic coatings, which have been successfully used to construct HAP-based fire-resistant paper with superior self-cleaning and oil-water separation capability, as well as sustainable Chinese Xuan paper with enhanced writing performance. Such mesoscale engineering, which unifies synthesis, assembly, and function, represents a new paradigm for creating robust, multifunctional biomimetic materials.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103263"},"PeriodicalIF":8.4,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412413","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}
Atmospheric CO2 removal at Gton scale is necessary to limit global temperature rise. This study provides essential insights into the energy, area, and water requirements of solid calcium looping for large-scale CO2 removal, combining experimental results with an upscaled system context. Thermogravimetric analysis (TGA) characterizes the products, while scanning electron microscopy (SEM) qualitatively assesses sorbent performance. Experiments in a climate chamber focus on carbonation kinetics, varying relative humidity, temperature, and slaking ratios.
Results demonstrate that relative humidity above 70 % significantly enhances carbonation rates, favoring the placement of facilities in high-humidity locations. The optimal slaking ratio is identified as one mole of water per mole of CaO. Carbonation at 20 °C yields faster reaction kinetics than at 12 °C, with both temperatures achieving a carbonation degree of 66 mol.% in three and four days, respectively. Lower temperatures require a larger area to achieve similar annual capture rates. Cyclic testing shows stable capture capacity and carbonation kinetics over nine cycles.
For a one-million-ton-per-year capture unit, the process requires 4.9–6.2 GJ/ton for electric heating, with air contactor areas reduced to 0.08–0.12 km using vertically stacked sorbent trays. Water consumption reaches 0.7 ton/ton at the optimal slaking ratio but can be minimized in high-humidity, water-scarce locations by omitting slaking, at the expense of larger area requirements.
While only northern Europe currently meets the conditions for implementing the technology, considering both electricity grid CO2 intensity and weather, the potential of solid calcium looping for large-scale CO2 removal remains promising, warranting further exploration of logistics and practicalities in real-world applications.
{"title":"Is solid calcium looping a scalable technology for mega-ton carbon dioxide removal?","authors":"M.M. Paulsen, S.G.R. Nielsen, F.J. Tilsted, T.H. Pedersen","doi":"10.1016/j.jcou.2025.103255","DOIUrl":"10.1016/j.jcou.2025.103255","url":null,"abstract":"<div><div>Atmospheric CO<sub>2</sub> removal at Gton scale is necessary to limit global temperature rise. This study provides essential insights into the energy, area, and water requirements of solid calcium looping for large-scale CO<sub>2</sub> removal, combining experimental results with an upscaled system context. Thermogravimetric analysis (TGA) characterizes the products, while scanning electron microscopy (SEM) qualitatively assesses sorbent performance. Experiments in a climate chamber focus on carbonation kinetics, varying relative humidity, temperature, and slaking ratios.</div><div>Results demonstrate that relative humidity above 70 % significantly enhances carbonation rates, favoring the placement of facilities in high-humidity locations. The optimal slaking ratio is identified as one mole of water per mole of CaO. Carbonation at 20 °C yields faster reaction kinetics than at 12 °C, with both temperatures achieving a carbonation degree of 66 mol.% in three and four days, respectively. Lower temperatures require a larger area to achieve similar annual capture rates. Cyclic testing shows stable capture capacity and carbonation kinetics over nine cycles.</div><div>For a one-million-ton-per-year capture unit, the process requires 4.9–6.2 GJ/ton<span><math><msub><mrow></mrow><mrow><mtext>CO2</mtext></mrow></msub></math></span> for electric heating, with air contactor areas reduced to 0.08–0.12 km<span><math><msup><mrow></mrow><mrow><mn>2</mn></mrow></msup></math></span> using vertically stacked sorbent trays. Water consumption reaches 0.7 ton<span><math><msub><mrow></mrow><mrow><mtext>H2O</mtext></mrow></msub></math></span>/ton<span><math><msub><mrow></mrow><mrow><mtext>CO2</mtext></mrow></msub></math></span> at the optimal slaking ratio but can be minimized in high-humidity, water-scarce locations by omitting slaking, at the expense of larger area requirements.</div><div>While only northern Europe currently meets the conditions for implementing the technology, considering both electricity grid CO<sub>2</sub> intensity and weather, the potential of solid calcium looping for large-scale CO<sub>2</sub> removal remains promising, warranting further exploration of logistics and practicalities in real-world applications.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103255"},"PeriodicalIF":8.4,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412423","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}
India, the third-largest contributor to global CO₂ emissions (∼8 %), faces significant challenges in implementing large-scale geological carbon storage (GCS) projects. While geological suitability is crucial, socio-economic factors also influence feasibility, especially in a densely populated country like India. Additionally, public awareness of carbon capture, and storage (CCS) remains limited, making safety a key consideration. Basalt-based GCS offers permanent CO₂ mineralization, providing a secure storage solution. The Deccan Volcanic Province (DVP), spanning ∼500,000 km², presents a significant opportunity for gigaton-scale CO₂ storage. While previous studies have demonstrated the proof-of-concept for CO₂ storage in the DVP, no attempt has been made to characterize specific sites for pilot-scale projects. This study employs a Multi-Criteria Decision-Making approach, integrating Analytic Hierarchy Process (AHP) and Fuzzy-AHP (FAHP) to assess CCS site suitability in the DVP. The efficiency of the AHP and FAHP models were further verified using Monte Carlo FAHP technique. Nine geological, hydrological, and infrastructural factors were analyzed to generate suitability maps. The study identifies the Saurashtra region in Gujarat, northern Madhya Pradesh, and the Mumbai-Pune-Nashik corridor as highly suitable zones. Sensitivity analysis highlights "distance to faults" and "basalt thickness" as most influential factors, with FAHP providing more robust site characterization. While these findings provide a framework for narrowing down potential CCS sites in this largely unexplored region, further investigations into geochemical properties, host rock mechanical strength, and seismic risks are essential. Finally, estimated CO₂ storage potential in suitable areas suggests substantial potential, enabling long-term storage and reducing the source-to-sink distance for major emitting regions.
{"title":"Identification of potential CO2 storage zones in the Deccan Volcanic Province using multi-criteria decision-making approaches","authors":"Dip Das , Gyan Prakash , Nimisha Vedanti , Jyotirmoy Mallik","doi":"10.1016/j.jcou.2025.103257","DOIUrl":"10.1016/j.jcou.2025.103257","url":null,"abstract":"<div><div>India, the third-largest contributor to global CO₂ emissions (∼8 %), faces significant challenges in implementing large-scale geological carbon storage (GCS) projects. While geological suitability is crucial, socio-economic factors also influence feasibility, especially in a densely populated country like India. Additionally, public awareness of carbon capture, and storage (CCS) remains limited, making safety a key consideration. Basalt-based GCS offers permanent CO₂ mineralization, providing a secure storage solution. The Deccan Volcanic Province (DVP), spanning ∼500,000 km², presents a significant opportunity for gigaton-scale CO₂ storage. While previous studies have demonstrated the proof-of-concept for CO₂ storage in the DVP, no attempt has been made to characterize specific sites for pilot-scale projects. This study employs a Multi-Criteria Decision-Making approach, integrating Analytic Hierarchy Process (AHP) and Fuzzy-AHP (FAHP) to assess CCS site suitability in the DVP. The efficiency of the AHP and FAHP models were further verified using Monte Carlo FAHP technique. Nine geological, hydrological, and infrastructural factors were analyzed to generate suitability maps. The study identifies the Saurashtra region in Gujarat, northern Madhya Pradesh, and the Mumbai-Pune-Nashik corridor as highly suitable zones. Sensitivity analysis highlights \"distance to faults\" and \"basalt thickness\" as most influential factors, with FAHP providing more robust site characterization. While these findings provide a framework for narrowing down potential CCS sites in this largely unexplored region, further investigations into geochemical properties, host rock mechanical strength, and seismic risks are essential. Finally, estimated CO₂ storage potential in suitable areas suggests substantial potential, enabling long-term storage and reducing the source-to-sink distance for major emitting regions.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103257"},"PeriodicalIF":8.4,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412422","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 : 2025-10-23DOI: 10.1016/j.jcou.2025.103252
Cheng Cao , Yu Li , Yulong Zhao , Shaomu Wen , Ye Tian , Liehui Zhang , Qingping Li , Shouwei Zhou , Deping Zhang , Lili Liu , Zhenglin Cao , Yong Hu
Injecting CO2 into carbonate hydrocarbon reservoirs can enhance gas recovery (EGR) and achieve carbon sequestration. However, the mechanism by which supercritical CO2-water-rock interactions alter carbonate wettability remains unclear. This study investigates Maokou Formation carbonates from the Wolonghe gas reservoir (Sichuan Basin, China) under reservoir conditions (85 °C, 55 MPa). Contact angle measurements, X-ray diffraction, scanning electron microscopy, and nuclear magnetic resonance were used to monitor wettability evolution. Numerical models were developed to assess the impact of wettability on gas recovery and CO2 sequestration. Results show that CO2-water-rock reactions cause significant changes in surface minerals and formation water. Extensive dolomite dissolution and subsequent precipitation of calcium carbonate and calcium sulfate occur. The abundance of hydrophilic minerals decrease, leading to a transition from hydrophilic to hydrophobic reservoir wettability. Prolonged reaction further diminishes water-wetness, while increased pore size due to dominant mineral dissolution reduces water retention and hydrophilicity. Simulations indicate that reduced hydrophilicity enhances CO2 structural trapping but decreases CO2 mobility and CH4 recovery efficiency. Residual, dissolution, and mineral trapping capacities also decline, increasing CO2 leakage risks and reducing sequestration safety. Therefore, maintaining water wettability is crucial for efficient and safe CO2-EGR operations. This study offers theoretical insights into CO2-water-rock interaction mechanisms affecting carbonate wettability and informs the integrated evaluation of CO2-enhanced recovery and sequestration strategies.
{"title":"The mechanism of wettability changes of carbonate rocks under supercritical CO2-water-rock interaction: Implications for CO2-enhanced gas recovery and geo-sequestration","authors":"Cheng Cao , Yu Li , Yulong Zhao , Shaomu Wen , Ye Tian , Liehui Zhang , Qingping Li , Shouwei Zhou , Deping Zhang , Lili Liu , Zhenglin Cao , Yong Hu","doi":"10.1016/j.jcou.2025.103252","DOIUrl":"10.1016/j.jcou.2025.103252","url":null,"abstract":"<div><div>Injecting CO<sub>2</sub> into carbonate hydrocarbon reservoirs can enhance gas recovery (EGR) and achieve carbon sequestration. However, the mechanism by which supercritical CO<sub>2</sub>-water-rock interactions alter carbonate wettability remains unclear. This study investigates Maokou Formation carbonates from the Wolonghe gas reservoir (Sichuan Basin, China) under reservoir conditions (85 °C, 55 MPa). Contact angle measurements, X-ray diffraction, scanning electron microscopy, and nuclear magnetic resonance were used to monitor wettability evolution. Numerical models were developed to assess the impact of wettability on gas recovery and CO<sub>2</sub> sequestration. Results show that CO<sub>2</sub>-water-rock reactions cause significant changes in surface minerals and formation water. Extensive dolomite dissolution and subsequent precipitation of calcium carbonate and calcium sulfate occur. The abundance of hydrophilic minerals decrease, leading to a transition from hydrophilic to hydrophobic reservoir wettability. Prolonged reaction further diminishes water-wetness, while increased pore size due to dominant mineral dissolution reduces water retention and hydrophilicity. Simulations indicate that reduced hydrophilicity enhances CO<sub>2</sub> structural trapping but decreases CO<sub>2</sub> mobility and CH<sub>4</sub> recovery efficiency. Residual, dissolution, and mineral trapping capacities also decline, increasing CO<sub>2</sub> leakage risks and reducing sequestration safety. Therefore, maintaining water wettability is crucial for efficient and safe CO<sub>2</sub>-EGR operations. This study offers theoretical insights into CO<sub>2</sub>-water-rock interaction mechanisms affecting carbonate wettability and informs the integrated evaluation of CO<sub>2</sub>-enhanced recovery and sequestration strategies.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103252"},"PeriodicalIF":8.4,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358950","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 : 2025-10-22DOI: 10.1016/j.jcou.2025.103250
Lei Feng , Chenxi Liu , Kun Zhang , Yinghuan Kuang , Jian Kang
With the acceleration of urbanization and improvement in residents' living standards, how to achieve efficient valorization of food waste has become an important research topic. This study addresses the low methane production efficiency in anaerobic digestion of starch-rich food waste. By employing targeted bioaugmentation with propionate-degrading methanogenic consortia, we constructed a multi-stage metabolic network regulated by “hydrogenotrophic methanogens as primary drivers, acetoclastic methanogens as secondary assistants, and hydrolytic bacteria for synergistic enhancement”. Experimental results demonstrate that the total biogas production reached its peak of 322.29 mL/g VS at a 10 % bioaugmentation dosage, representing a 19 % increase compared to the control group (SK), while methane production reached 107.63 mL/g VS, 1.28 times that of SK. Mechanistic analysis reveals that: (1) The bioaugmented consortium rapidly enriches hydrogenotrophic methanogens (Methanobacterium) and acetoclastic methanogens (Methanosaeta) through “competitive exclusion effects”, establishing dual-pathway synergistic metabolism of CO₂/H₂-to-methane and acetate-to-methane; (2) Syntrophomonadia and Methanobacterium form a hydrogen-acetate cross-feeding relationship: the former oxidizes acetic acid to produce H₂/CO₂, while the latter selectively utilizes low-concentration H₂ to enhance overall metabolic efficiency. This study provides an effective microbial community regulation strategy and engineering references for food waste resource recovery.
{"title":"Efficient valorization of starch-rich food waste for methane recovery: Targeted bioaugmentation of propionate-degrading methanogenic consortia and synergistically regulated metabolic networks","authors":"Lei Feng , Chenxi Liu , Kun Zhang , Yinghuan Kuang , Jian Kang","doi":"10.1016/j.jcou.2025.103250","DOIUrl":"10.1016/j.jcou.2025.103250","url":null,"abstract":"<div><div>With the acceleration of urbanization and improvement in residents' living standards, how to achieve efficient valorization of food waste has become an important research topic. This study addresses the low methane production efficiency in anaerobic digestion of starch-rich food waste. By employing targeted bioaugmentation with propionate-degrading methanogenic consortia, we constructed a multi-stage metabolic network regulated by “hydrogenotrophic methanogens as primary drivers, acetoclastic methanogens as secondary assistants, and hydrolytic bacteria for synergistic enhancement”. Experimental results demonstrate that the total biogas production reached its peak of 322.29 mL/g VS at a 10 % bioaugmentation dosage, representing a 19 % increase compared to the control group (SK), while methane production reached 107.63 mL/g VS, 1.28 times that of SK. Mechanistic analysis reveals that: (1) The bioaugmented consortium rapidly enriches hydrogenotrophic methanogens (<em>Methanobacterium</em>) and acetoclastic methanogens (<em>Methanosaeta</em>) through “competitive exclusion effects”, establishing dual-pathway synergistic metabolism of CO₂/H₂-to-methane and acetate-to-methane; (2) <em>Syntrophomonadia</em> and <em>Methanobacterium</em> form a hydrogen-acetate cross-feeding relationship: the former oxidizes acetic acid to produce H₂/CO₂, while the latter selectively utilizes low-concentration H₂ to enhance overall metabolic efficiency. This study provides an effective microbial community regulation strategy and engineering references for food waste resource recovery.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103250"},"PeriodicalIF":8.4,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358948","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 : 2025-10-21DOI: 10.1016/j.jcou.2025.103254
Aiping Wang , Hongxia Liu , Yifan Yue , Lingfeng Mao , Baohe Wang , Jing Ma , Jing Zhu , Zhongfeng Geng
The ethylene methoxycarbonylation reaction catalyzed by trinuclear ruthenium clusters using CO2 as the C1 source represents a promising approach for methyl propionate (MeP) synthesis. However, the precise active sites and catalytic mechanism of these versatile catalysts remain incompletely understood. Herein, various ionic liquids (ILs) featuring diverse cationic frameworks and electron-donating groups were synthesized and employed to construct IL-modified trinuclear ruthenium cluster catalysts system (ILM-Ru₃). The investigation into the evolution of active species and the sequential catalytic mechanism during the integrated methoxycarbonylation of ethylene, CO₂, and methanol towards MeP was conducted through experimental and density functional theory (DFT) methods. The results indicated that the cationic framework's structure influences coordination sites and active species distribution. The catalytic activity strongly correlated with the electron-donating capability of cations and the proton-binding capacity of anions. Remarkably, the ILM-Ru₃ system achieved a significantly improved performance (TON=39.8 vs TON=13.7 and selectivity 80.5 % vs 28.2 %) with ≤ 6 % activity variation across 7 cycles outperforming the unmodified system. Complementary spectroscopic techniques including FT-IR, XPS, and 1H/13C NMR, along with quantum chemistry analysis, provided evidence of carbene–Ru coordination and unveiled the evolution of various Ru-H species. A unique synergistic catalytic mechanism of IRM-Ru3 enhanced CO₂-integrated methoxycarbonylation that avoids Ru₃(CO)₁₁ regeneration and minimizes cluster dissociation has been proposed, which deeply demonstrating the internal reasons of the improvement in catalytic performance. This approach provides theoretical guidance for the rational design of ruthenium cluster catalysts and development of a green and sustainable MeP process.
以CO2为C1源，三核钌簇催化乙烯甲氧羰基化反应是合成丙酸甲酯（MeP）的一种很有前途的方法。然而，这些多功能催化剂的确切活性位点和催化机理仍不完全清楚。本文合成了具有不同阳离子框架和供电子基团的多种离子液体（ILs），并利用其构建了il修饰的三核钌簇催化剂体系（ILM-Ru₃）。通过实验和密度泛函理论（DFT）研究了乙烯、CO 2和甲醇甲氧羰基化合成MeP过程中活性物质的演化和顺序催化机理。结果表明，阳离子骨架的结构影响配位位点和活性物种的分布。催化活性与阳离子的给电子能力和阴离子的质子结合能力密切相关。值得注意的是，ILM-Ru₃系统取得了显着改善的性能（TON=39.8 vs TON=13.7，选择性80.5 % vs 28.2 %），7个循环的活性变化≤ 6 %，优于未修饰的系统。互补光谱技术包括FT-IR、XPS和1H/13C NMR，以及量子化学分析，提供了碳-钌配位的证据，揭示了各种钌-氢物质的进化。提出了一种独特的IRM-Ru3增强CO₂集成甲氧羰基化协同催化机理，避免了Ru₃（CO）₁₁再生，最大限度地减少了簇解离，深刻揭示了催化性能提高的内在原因。该方法为合理设计钌簇催化剂和开发绿色可持续的MeP工艺提供了理论指导。
{"title":"Synergistic catalysis: Ionic liquid-modified trinuclear ruthenium clusters enhanced CO2-integrated methoxycarbonylation of ethylene","authors":"Aiping Wang , Hongxia Liu , Yifan Yue , Lingfeng Mao , Baohe Wang , Jing Ma , Jing Zhu , Zhongfeng Geng","doi":"10.1016/j.jcou.2025.103254","DOIUrl":"10.1016/j.jcou.2025.103254","url":null,"abstract":"<div><div>The ethylene methoxycarbonylation reaction catalyzed by trinuclear ruthenium clusters using CO<sub>2</sub> as the C1 source represents a promising approach for methyl propionate (MeP) synthesis. However, the precise active sites and catalytic mechanism of these versatile catalysts remain incompletely understood. Herein, various ionic liquids (ILs) featuring diverse cationic frameworks and electron-donating groups were synthesized and employed to construct IL-modified trinuclear ruthenium cluster catalysts system (ILM-Ru₃). The investigation into the evolution of active species and the sequential catalytic mechanism during the integrated methoxycarbonylation of ethylene, CO₂, and methanol towards MeP was conducted through experimental and density functional theory (DFT) methods. The results indicated that the cationic framework's structure influences coordination sites and active species distribution. The catalytic activity strongly correlated with the electron-donating capability of cations and the proton-binding capacity of anions. Remarkably, the ILM-Ru₃ system achieved a significantly improved performance (TON=39.8 vs TON=13.7 and selectivity 80.5 % vs 28.2 %) with ≤ 6 % activity variation across 7 cycles outperforming the unmodified system. Complementary spectroscopic techniques including FT-IR, XPS, and <sup>1</sup>H/<sup>13</sup>C NMR, along with quantum chemistry analysis, provided evidence of carbene–Ru coordination and unveiled the evolution of various Ru-H species. A unique synergistic catalytic mechanism of IRM-Ru<sub>3</sub> enhanced CO₂-integrated methoxycarbonylation that avoids Ru₃(CO)₁₁ regeneration and minimizes cluster dissociation has been proposed, which deeply demonstrating the internal reasons of the improvement in catalytic performance. This approach provides theoretical guidance for the rational design of ruthenium cluster catalysts and development of a green and sustainable MeP process.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103254"},"PeriodicalIF":8.4,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358949","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}
In this study, we investigate the use of hydrogen bond-stabilized amine-based mixtures (a class of systems hereafter referred to as Hydrogen Bond-Stabilized Mixtures, HBSMs; e.g., n-butylamine with glycerol or guanidinium chloride) as an alternative approach to improve carbon dioxide capture efficiency while avoiding massive solvent evaporation. CO2 capture experiments reveal that these mixtures exhibit improved sorption capacity compared to pure amines, while the presence of hydrogen bond acceptors plays a crucial role in stabilizing the systems, due to the establishment of an extended hydrogen-bond network. ATR-IR analyses confirm that CO2 capture occurs through a combination of physical and chemical absorption; on the other hand, TGA data reveal a substantial reduction in solvent evaporation rates, particularly in the n-butylamine/glycerol mixture, where evaporation decreased by more than an order of magnitude compared to pure amine. The high CO2 absorption capacity and reduced amine volatility of these mixtures open a promising avenue for more sustainable and energy-efficient carbon capture technologies, paving the way for relevant industrial applications.
{"title":"Hydrogen bond-stabilized mixtures for efficient carbon dioxide capture","authors":"Joaquín Arata Badano , Giuseppe Ferraro , Daniele Motta , Claudia Barolo , Sergio Bocchini , Jorge Gustavo Uranga , Matteo Bonomo","doi":"10.1016/j.jcou.2025.103249","DOIUrl":"10.1016/j.jcou.2025.103249","url":null,"abstract":"<div><div>In this study, we investigate the use of hydrogen bond-stabilized amine-based mixtures (a class of systems hereafter referred to as Hydrogen Bond-Stabilized Mixtures, HBSMs; e.g., n-butylamine with glycerol or guanidinium chloride) as an alternative approach to improve carbon dioxide capture efficiency while avoiding massive solvent evaporation. CO<sub>2</sub> capture experiments reveal that these mixtures exhibit improved sorption capacity compared to pure amines, while the presence of hydrogen bond acceptors plays a crucial role in stabilizing the systems, due to the establishment of an extended hydrogen-bond network. ATR-IR analyses confirm that CO<sub>2</sub> capture occurs through a combination of physical and chemical absorption; on the other hand, TGA data reveal a substantial reduction in solvent evaporation rates, particularly in the n-butylamine/glycerol mixture, where evaporation decreased by more than an order of magnitude compared to pure amine. The high CO<sub>2</sub> absorption capacity and reduced amine volatility of these mixtures open a promising avenue for more sustainable and energy-efficient carbon capture technologies, paving the way for relevant industrial applications.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103249"},"PeriodicalIF":8.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145321282","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 : 2025-10-17DOI: 10.1016/j.jcou.2025.103243
Simon Lukato , Agnieszka Krogul-Sobczak , Grzegorz Litwinienko , Ola F. Wendt , Reine Wallenberg , Filip Hallböök , Michal Wojcik
In the pursuit of CO₂-neutral renewable energy solutions, biofuels have emerged as one of the key strategies. However, biodiesel production generates a surplus of crude glycerol (GL), creating a need for efficient valorization pathways. The conversion of GL into value-added chemicals represents a sustainable approach to address this issue. Metal nanoclusters (NCats) embedded within metal-organic frameworks (MOFs) constitute a promising class of hybrid catalysts for GL–CO₂ coupling, yet their controlled synthesis remains limited to a few MOF systems. Herein, we present a clean, scalable, and efficient method for the synthesis of ultra-small, surfactant-free Cu, Ag, and Pd NCats encapsulated in cerium-based MOFs. The resulting catalysts were evaluated in the direct carboxylation of crude GL with CO₂. Among them, the Pd₁Cu₁@MOF1 composite demonstrated outstanding performance, achieving > 73 % yield and a TOF > 100 h⁻¹ with pure GL, and > 14 % yield with a TOF of 30 h⁻¹ using crude GL. The method also enabled successful incorporation of trimetallic PdAgCu NCats, highlighting its potential for the sustainable synthesis of multimetallic NCats-MOF catalytic systems.
{"title":"Green and scalable approaches for synthesis and encapsulating clean metal nanoclusters inside cerium MOFs for efficient glycerol carboxylation with CO2","authors":"Simon Lukato , Agnieszka Krogul-Sobczak , Grzegorz Litwinienko , Ola F. Wendt , Reine Wallenberg , Filip Hallböök , Michal Wojcik","doi":"10.1016/j.jcou.2025.103243","DOIUrl":"10.1016/j.jcou.2025.103243","url":null,"abstract":"<div><div>In the pursuit of CO₂-neutral renewable energy solutions, biofuels have emerged as one of the key strategies. However, biodiesel production generates a surplus of crude glycerol (GL), creating a need for efficient valorization pathways. The conversion of GL into value-added chemicals represents a sustainable approach to address this issue. Metal nanoclusters (NCats) embedded within metal-organic frameworks (MOFs) constitute a promising class of hybrid catalysts for GL–CO₂ coupling, yet their controlled synthesis remains limited to a few MOF systems. Herein, we present a clean, scalable, and efficient method for the synthesis of ultra-small, surfactant-free Cu, Ag, and Pd NCats encapsulated in cerium-based MOFs. The resulting catalysts were evaluated in the direct carboxylation of crude GL with CO₂. Among them, the Pd₁Cu₁@MOF1 composite demonstrated outstanding performance, achieving > 73 % yield and a TOF > 100 h⁻¹ with pure GL, and > 14 % yield with a TOF of 30 h⁻¹ using crude GL. The method also enabled successful incorporation of trimetallic PdAgCu NCats, highlighting its potential for the sustainable synthesis of multimetallic NCats-MOF catalytic systems.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103243"},"PeriodicalIF":8.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145321281","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 : 2025-10-17DOI: 10.1016/j.jcou.2025.103248
Nathalie E.G. Ligthart , Mohammed A. Khan , Johan T. Padding , David A. Vermaas
Electrochemical conversion of CO2 to hydrocarbons is limited by the low solubility and slow transport of CO2 in aqueous systems. We demonstrate that we can reach partial current densities for CO2-to-CO of 40 mA/cm2 in fully aqueous systems, without the use of gas diffusion electrodes. We alleviate the mass transfer limitation by combining a suspension of catalytically active silver nanoparticles (Ag NPs) with a flow-through current collector. This extends the reactive area into the electrolyzer channel and improves the accessibility of dissolved CO2 in a larger volume of electrolyte. The flow-through electrode system also outperforms a fully suspended electrode (based on carbon black particles), due to enhanced electric conductivity and smaller carbon area to minimize parasitic side-reactions. Additionally, we show that the distribution of the Ag NPs is pivotal for high CO2 conversion rates, demonstrated by the highest CO current density obtained when a suspension of Ag NPs and SDS as surfactant is flowing through the 3D electrodes as pre-treatment. A stable CO current density can be sustained for more than 4 h. Although the conversion rate is still moderate compared to gas-fed CO2 electrolzyers, the partial current density for flow-through electrodes is more than an order of magnitude larger than for planar flow systems. This work shows that CO2 conversion in aqueous systems can be enhanced considerably by exploiting larger electrolyte volumes via smart electrode designs, such as a flow-through principle.
{"title":"Flow-through electrodes enable order of magnitude higher partial current densities in aqueous CO2 electrolysis","authors":"Nathalie E.G. Ligthart , Mohammed A. Khan , Johan T. Padding , David A. Vermaas","doi":"10.1016/j.jcou.2025.103248","DOIUrl":"10.1016/j.jcou.2025.103248","url":null,"abstract":"<div><div>Electrochemical conversion of CO<sub>2</sub> to hydrocarbons is limited by the low solubility and slow transport of CO<sub>2</sub> in aqueous systems. We demonstrate that we can reach partial current densities for CO<sub>2</sub>-to-CO of 40 mA/cm<sup>2</sup> in fully aqueous systems, without the use of gas diffusion electrodes. We alleviate the mass transfer limitation by combining a suspension of catalytically active silver nanoparticles (Ag NPs) with a flow-through current collector. This extends the reactive area into the electrolyzer channel and improves the accessibility of dissolved CO<sub>2</sub> in a larger volume of electrolyte. The flow-through electrode system also outperforms a fully suspended electrode (based on carbon black particles), due to enhanced electric conductivity and smaller carbon area to minimize parasitic side-reactions. Additionally, we show that the distribution of the Ag NPs is pivotal for high CO<sub>2</sub> conversion rates, demonstrated by the highest CO current density obtained when a suspension of Ag NPs and SDS as surfactant is flowing through the 3D electrodes as pre-treatment. A stable CO current density can be sustained for more than 4 h. Although the conversion rate is still moderate compared to gas-fed CO<sub>2</sub> electrolzyers, the partial current density for flow-through electrodes is more than an order of magnitude larger than for planar flow systems. This work shows that CO<sub>2</sub> conversion in aqueous systems can be enhanced considerably by exploiting larger electrolyte volumes via smart electrode designs, such as a flow-through principle.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"102 ","pages":"Article 103248"},"PeriodicalIF":8.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145321280","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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