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Understanding the role of pressurized CO2 in the direct recycling process of Li-ion battery positive electrode
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-15 DOI: 10.1016/j.jcou.2025.103080
Neil Hayagan , Pierre Guillou , Jacob Olchowka , Fatma Ercicek , Carole Lecoutre , Olivier Nguyen , Cyril Aymonier , Samuel Marre , Arnaud Erriguible , Gilles Philippot
The ternary mixture of carbon dioxide (CO2), triethyl phosphate (TEP), and acetone enabled an efficient delamination of Li-ion battery (LIB) positive electrode inciting an interest to study the ternary mixture behavior. Pressurized fluids, such as CO2, are known to be beneficial in various chemical processes. However, the behavior of CO2, when mixed with TEP and acetone is not well understood, particularly under pressure and temperature conditions. This study investigates the behavior of CO2 or nitrogen (N2) in mixtures with TEP and acetone at various compositions, using experimental investigations of the ternary system. Experimental data covers four temperatures at 35°C, 70°C, 100°C and 120°C at a constant pressure of 100 bar. The phase behaviors of the binary and ternary mixtures were observed using a transparent reactor, while the compositions were analyzed in situ with Raman spectroscopy. Under isobaric conditions, a single phase was observed with CO2 at 35°C, both in the binary systems with either TEP or acetone, as well as in the ternary mixture. In contrast, a biphasic system was observed at higher temperatures (70°C, 100°C, and 120°C) in all mixtures containing CO2. Specifically, the biphasic condition at 55°C at 100 bar, of the mixtures were semi-quantitatively investigated using Raman spectroscopy to probe the compositions in the vapor and liquid phases. These observations elucidate the crucial role of CO2 in the delamination of the positive electrode in LIB using the TEP-acetone-CO2 system enabling high efficiency, low solvent consumption, and a faster processing time.
{"title":"Understanding the role of pressurized CO2 in the direct recycling process of Li-ion battery positive electrode","authors":"Neil Hayagan ,&nbsp;Pierre Guillou ,&nbsp;Jacob Olchowka ,&nbsp;Fatma Ercicek ,&nbsp;Carole Lecoutre ,&nbsp;Olivier Nguyen ,&nbsp;Cyril Aymonier ,&nbsp;Samuel Marre ,&nbsp;Arnaud Erriguible ,&nbsp;Gilles Philippot","doi":"10.1016/j.jcou.2025.103080","DOIUrl":"10.1016/j.jcou.2025.103080","url":null,"abstract":"<div><div>The ternary mixture of carbon dioxide (CO<sub>2</sub>), triethyl phosphate (TEP), and acetone enabled an efficient delamination of Li-ion battery (LIB) positive electrode inciting an interest to study the ternary mixture behavior. Pressurized fluids, such as CO<sub>2</sub>, are known to be beneficial in various chemical processes. However, the behavior of CO<sub>2</sub>, when mixed with TEP and acetone is not well understood, particularly under pressure and temperature conditions. This study investigates the behavior of CO<sub>2</sub> or nitrogen (N<sub>2</sub>) in mixtures with TEP and acetone at various compositions, using experimental investigations of the ternary system. Experimental data covers four temperatures at 35°C, 70°C, 100°C and 120°C at a constant pressure of 100 bar. The phase behaviors of the binary and ternary mixtures were observed using a transparent reactor, while the compositions were analyzed <em>in situ</em> with Raman spectroscopy. Under isobaric conditions, a single phase was observed with CO<sub>2</sub> at 35°C, both in the binary systems with either TEP or acetone, as well as in the ternary mixture. In contrast, a biphasic system was observed at higher temperatures (70°C, 100°C, and 120°C) in all mixtures containing CO<sub>2</sub>. Specifically, the biphasic condition at 55°C at 100 bar, of the mixtures were semi-quantitatively investigated using Raman spectroscopy to probe the compositions in the vapor and liquid phases. These observations elucidate the crucial role of CO<sub>2</sub> in the delamination of the positive electrode in LIB using the TEP-acetone-CO<sub>2</sub> system enabling high efficiency, low solvent consumption, and a faster processing time.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103080"},"PeriodicalIF":7.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834080","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}
引用次数: 0
Investigation of thermal effects and transient reactor profiles in a plasma-sorbent system for simultaneous CO2 capture and conversion
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-15 DOI: 10.1016/j.jcou.2025.103081
Huub van den Bogaard , Ludovica Villantieri , Pierdomenico Biasi , Fausto Gallucci , Sirui Li
CO2 capture and utilisation (CCU) is a promising solution to mitigate greenhouse gas emissions and has received much attention recently. Usually, CO2 is captured and utilised in two separate processes. In this work, we focus on integrating both processes in one single unit using a non-thermal plasma reactor packed with zeolite 5 A as the CO2 sorbent. CO2 adsorbed by the sorbent can be desorbed and simultaneously activated by applying a plasma over the sorbent bed. In such case, the plasma-sorbent system demonstrated a transient behaviour including the variation of CO2 concentration, plasma power and reactor temperature. This work aims to understand such behaviour better and to optimise the process by selecting a suitable desorption duration. To study the time-resolved radial temperature profiles and to highlight the effect of in situ CO2 conversion on CO2 desorption rate, a 2D phenomenological reactor model was developed. This model predicts heating and desorption behaviour in two different cases: 1) heating from a central heating rod, and 2) heating from the bulk of the sorbent bed with a fixed conversion that is provided as a modelling input. The first case represents temperature swing adsorption (TSA), while the latter represents the heating effect in the case of plasma-assisted desorption. Experiments were also conducted to verify the model and investigate the desorption and conversion of CO2. The results showed that in situ CO2 conversion during plasma-assisted desorption increases the desorption rate compared to TSA. Thermal desorption plays an important role in the plasma-induced desorption of CO2, and a more uniform radial temperature profile can be achieved compared to using a central heating rod. In addition, it was observed that CO2 conversion stagnates after 4 minutes of plasma exposure. Longer exposure times did not lead to higher CO2 conversions because the reverse reaction of O2 and CO to CO2 competed with the forward reaction. Although plasma-induced desorption has a much higher energy consumption compared to TSA, 14.5 % CO2 conversion can be achieved during the desorption process, and shorter cycle times can be achieved because of the faster desorption rate.
{"title":"Investigation of thermal effects and transient reactor profiles in a plasma-sorbent system for simultaneous CO2 capture and conversion","authors":"Huub van den Bogaard ,&nbsp;Ludovica Villantieri ,&nbsp;Pierdomenico Biasi ,&nbsp;Fausto Gallucci ,&nbsp;Sirui Li","doi":"10.1016/j.jcou.2025.103081","DOIUrl":"10.1016/j.jcou.2025.103081","url":null,"abstract":"<div><div>CO<sub>2</sub> capture and utilisation (CCU) is a promising solution to mitigate greenhouse gas emissions and has received much attention recently. Usually, CO<sub>2</sub> is captured and utilised in two separate processes. In this work, we focus on integrating both processes in one single unit using a non-thermal plasma reactor packed with zeolite 5 A as the CO<sub>2</sub> sorbent. CO<sub>2</sub> adsorbed by the sorbent can be desorbed and simultaneously activated by applying a plasma over the sorbent bed. In such case, the plasma-sorbent system demonstrated a transient behaviour including the variation of CO<sub>2</sub> concentration, plasma power and reactor temperature. This work aims to understand such behaviour better and to optimise the process by selecting a suitable desorption duration. To study the time-resolved radial temperature profiles and to highlight the effect of in situ CO<sub>2</sub> conversion on CO<sub>2</sub> desorption rate, a 2D phenomenological reactor model was developed. This model predicts heating and desorption behaviour in two different cases: 1) heating from a central heating rod, and 2) heating from the bulk of the sorbent bed with a fixed conversion that is provided as a modelling input. The first case represents temperature swing adsorption (TSA), while the latter represents the heating effect in the case of plasma-assisted desorption. Experiments were also conducted to verify the model and investigate the desorption and conversion of CO<sub>2</sub>. The results showed that in situ CO<sub>2</sub> conversion during plasma-assisted desorption increases the desorption rate compared to TSA. Thermal desorption plays an important role in the plasma-induced desorption of CO<sub>2</sub>, and a more uniform radial temperature profile can be achieved compared to using a central heating rod. In addition, it was observed that CO<sub>2</sub> conversion stagnates after 4 minutes of plasma exposure. Longer exposure times did not lead to higher CO<sub>2</sub> conversions because the reverse reaction of O<sub>2</sub> and CO to CO<sub>2</sub> competed with the forward reaction. Although plasma-induced desorption has a much higher energy consumption compared to TSA, 14.5 % CO<sub>2</sub> conversion can be achieved during the desorption process, and shorter cycle times can be achieved because of the faster desorption rate.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103081"},"PeriodicalIF":7.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834081","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}
引用次数: 0
Product Environmental Footprint in the construction sector – Proposal and assessment of a representative product for carbon-reinforced concrete
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-14 DOI: 10.1016/j.jcou.2025.103078
Pamela Haverkamp, Laura Schmidt, Jana Gerta Backes, Marzia Traverso
In this study, a representative product for carbon-reinforced concrete (CRC) in Germany is proposed according to the Product Environmental Footprint (PEF) method by the European Commission. Following the objectives of the PEF method, the main goal is to enhance comparability with other studies and promote transparency regarding the environmental performance of products. A CRC façade panel was chosen as the representative product based on insights from German market statistics and sectorial stakeholders. Furthermore, a PEF study was conducted for the defined product. Based on this study, the main environmental hotspots according to PEF are identified – most relevant impact categories, life cycle stages, processes and elementary flows. For instance, the most relevant impact categories were found to be Human Toxicity, cancer, Climate Change, and Resource Use, fossils. For each of these impact categories the most relevant processes and elementary flows were determined. Moreover, the most relevant life cycle was found to be the raw material extraction and pre-processing. An innovative aspect of this study is related to the calculation of the environmental impacts at the end of life. For the first time, the Circular Footprint Formula introduced in the PEF method is applied in the context of CRC. In this regard, a baseline and an alternative scenario are explored. In general, the outcomes of this study are a first step towards the application of the PEF methodology in the context of CRC and create a basis that fosters comparability and transparency in environmental assessments for CRC.
{"title":"Product Environmental Footprint in the construction sector – Proposal and assessment of a representative product for carbon-reinforced concrete","authors":"Pamela Haverkamp,&nbsp;Laura Schmidt,&nbsp;Jana Gerta Backes,&nbsp;Marzia Traverso","doi":"10.1016/j.jcou.2025.103078","DOIUrl":"10.1016/j.jcou.2025.103078","url":null,"abstract":"<div><div>In this study, a representative product for carbon-reinforced concrete (CRC) in Germany is proposed according to the Product Environmental Footprint (PEF) method by the European Commission. Following the objectives of the PEF method, the main goal is to enhance comparability with other studies and promote transparency regarding the environmental performance of products. A CRC façade panel was chosen as the representative product based on insights from German market statistics and sectorial stakeholders. Furthermore, a PEF study was conducted for the defined product. Based on this study, the main environmental hotspots according to PEF are identified – most relevant impact categories, life cycle stages, processes and elementary flows. For instance, the most relevant impact categories were found to be Human Toxicity, cancer, Climate Change, and Resource Use, fossils. For each of these impact categories the most relevant processes and elementary flows were determined. Moreover, the most relevant life cycle was found to be the raw material extraction and pre-processing. An innovative aspect of this study is related to the calculation of the environmental impacts at the end of life. For the first time, the Circular Footprint Formula introduced in the PEF method is applied in the context of CRC. In this regard, a baseline and an alternative scenario are explored. In general, the outcomes of this study are a first step towards the application of the PEF methodology in the context of CRC and create a basis that fosters comparability and transparency in environmental assessments for CRC.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103078"},"PeriodicalIF":7.2,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826367","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}
引用次数: 0
Circularity within carbon capture networks: A review of capture and utilization technologies
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-11 DOI: 10.1016/j.jcou.2025.103075
Ikhlas Ghiat , Aliya Banu , Yusuf Bicer , Abdulkarem I. Amhamed , Tareq Al-Ansari
The carbon circular economy, through carbon capture and utilization or storage (CCUS), represents a transformative approach with the capacity to create closed loop systems where CO2 emissions can be captured, stored or converted into value-added products, thereby reducing the dependency on fossil fuels and minimizing waste. This review comprehensively examines CCUS technologies within the context of circular economy to study their viability in a wider range. Diverse carbon sources, encompassing atmospheric, biomass and fossil-fuel derived carbon, are reviewed. Major carbon capture technologies are discussed through the dual lens of technology readiness level and economic viability. This work also extends to the review of various carbon storage options in geological formations and direct and indirect utilization routes. Moreover, carbon tax and policies favouring the implementation of CCUS into the circular economy are discussed. This study identifies diverse technological, economic, and regulatory limitations associated with CCUS and underscores the need for significant advancements to deploy these technologies at scale. To reach net-zero emissions by 2050, a portfolio approach with immediate implementation is necessary. Moreover, consolidated frameworks for assessment and monitoring, policy support, and international cooperation hold the potential to advance the adoption of this technology within a circular economy. This study provides important insights into the application of the circular economy concept into CCUS technologies to advance their large-scale deployment. Furthermore, it examines how CCUS technologies and circular economy practices can strengthen each other. As a result, this work highlights the circularisation of CCUS systems and the decarbonisation of circular economy.
通过碳捕集与利用或碳封存(CCUS)实现的碳循环经济是一种变革性方法,有能力创建闭环系统,将二氧化碳排放捕集、封存或转化为高附加值产品,从而减少对化石燃料的依赖并最大限度地减少浪费。本综述在循环经济的背景下全面考察了 CCUS 技术,以研究其在更大范围内的可行性。综述了各种碳源,包括大气碳、生物质碳和化石燃料衍生碳。从技术准备水平和经济可行性的双重角度讨论了主要的碳捕集技术。这项工作还包括审查地质构造中的各种碳储存方案以及直接和间接利用途径。此外,还讨论了有利于在循环经济中实施 CCUS 的碳税和政策。本研究指出了与 CCUS 相关的各种技术、经济和监管限制,并强调了大规模部署这些技术所需的重大进展。为了到 2050 年实现净零排放,有必要采取立即实施的组合方法。此外,评估与监测、政策支持和国际合作的综合框架有可能推动在循环经济中采用这种技术。本研究为将循环经济概念应用于 CCUS 技术以推动其大规模部署提供了重要见解。此外,它还探讨了 CCUS 技术和循环经济实践如何能够相互促进。因此,这项工作强调了 CCUS 系统的循环化和循环经济的去碳化。
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引用次数: 0
High-temperature slag engineering in pursuit of effective mineral carbonation of pyroxene-rich ferronickel slag 高温炉渣工程,追求富辉石镍铁炉渣的有效矿物碳化
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-11 DOI: 10.1016/j.jcou.2025.103077
Arne Peys , Natalia Pires Martins , Fernando Prado Araujo , Konstantinos Komnitsas , Peter Nielsen
The search for resources for low-carbon construction materials and valorization pathways for industrial residues go hand in hand. Mineral carbonation has been abundantly studied to strive for a net-zero CO2 construction sector. Ferronickel slags have been studied for the production of other cementitious materials, but have inferior carbonation potential due to their low Ca-content. This work shows that the reactivity of a pyroxene-rich ferronickel slag towards CO2 can be substantially increased using high-temperature slag engineering. Using a combination of CaCO3 additions and slow cooling, the produced compacts made from synthesized slags acquire a compressive strength of 30–40 MPa after carbonation at 10 bar CO2 and 60 °C for 16 hours. The reactivity towards CO2 originates from the formation of akermanite (Ca2MgSi2O7) during slag modification with > 20 wt% CaCO3. The compressive strength is dependent on the particle size distribution of the modified slag and carbonation time. Although the reaction degree of akermanite is high after 6 hours of carbonation, a significant strength increase is still seen after carbonation for 16 and 48 hours. The carbonation process forms a binding phase composed of aragonite and a CaMg-carbonate which might be high Mg-calcite or protodolomite. The CO2 balance of the overall process shows a substantially lower value compared to Portland clinker-based cements, but additional efforts are required to develop an optimum net-zero CO2 process.
寻找低碳建筑材料资源和工业残渣的价值化途径是相辅相成的。为努力实现二氧化碳净零排放的建筑行业,对矿物碳化进行了大量研究。铁镍矿渣已被研究用于生产其他胶凝材料,但由于其钙含量低,碳化潜力较差。这项研究表明,利用高温炉渣工程可以大幅提高富含辉石的镍铁合金炉渣对二氧化碳的反应性。通过添加 CaCO3 和缓慢冷却相结合的方法,在 10 bar CO2 和 60 °C 下碳化 16 小时后,由合成炉渣制成的压实物可获得 30-40 MPa 的抗压强度。对 CO2 的反应性源于炉渣改性过程中形成的赤铁矿(Ca2MgSi2O7)。抗压强度取决于改性炉渣的粒度分布和碳化时间。虽然碳化 6 小时后赤铁矿的反应程度较高,但碳化 16 和 48 小时后强度仍有显著提高。碳化过程形成了由文石和钙镁碳酸盐组成的结合相,后者可能是高镁方解石或原多罗莫石。与基于波特兰熟料的水泥相比,整个工艺的二氧化碳平衡值要低得多,但要开发出最佳的净零二氧化碳工艺还需要更多的努力。
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引用次数: 0
Insights into the reactivity of Ni-La catalysts for CO2 methanation
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-05 DOI: 10.1016/j.jcou.2025.103076
Luca Consentino , Miriam González-Castaño , Nuría Garcia-Moncada , Luis F. Bobadilla , Michelangelo Gruttadauria , Leonarda Francesca Liotta , José Antonio Odriozola
Efficient catalysts are essential for CO2 methanation reaction, a key process for sustainable energy applications. This study investigates the structural and chemical properties of Ni-La perovskite-based catalysts synthesized via one-pot and impregnation methods by microwave-assisted synthesis to improve Ni dispersion and phase homogeneity. Reduction temperature emerges as a key factor influencing catalyst structure and performance. Catalysts reduced at lower temperatures retain perovskite structures, leading to enhanced metal-support interactions, which are crucial for CO₂ activation and methane production. In contrast, higher reduction temperatures decompose the perovskite phase into metallic Ni and La₂O₃, which alters the catalytic behavior. The impregnation method enhances Ni dispersion, leading to higher metallic Ni availability and superior catalytic performance. Oxygen vacancies and carbonate species formed on the catalyst surface are identified as central to the reaction mechanism, facilitating CO₂ adsorption and conversion. This research underscores the importance of structure-to-function relationships, focusing on how synthesis methods and reduction conditions shape surface species generation and CO2 methanation rates. These insights advance the design of highly efficient catalysts for CO2 conversion, addressing environmental challenges and fostering sustainable energy solutions.
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引用次数: 0
Machine learning integration in thermodynamics: Predicting CO2 mixture saturation properties for sustainable refrigeration applications
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-04 DOI: 10.1016/j.jcou.2025.103072
Carlos G. Albà , Ismail I.I. Alkhatib , Lourdes F. Vega , Fèlix Llovell
The need for sustainable alternatives in refrigeration has grown as Europe enforces mandates on avoiding high global warming potential (GWP) refrigerants. CO₂-based refrigerants have emerged as a promising choice in response, distinguished by its low GWP and reduced flammability, compared to formulated hydrofluoroolefins, thus offering a safer and sustainable solution in the context of next generation drop-in refrigerants. This study presents a machine-learning-based methodology to estimate the saturation properties of CO2-based mixtures, allowing for the precise tuning of molecular-based models like the polar soft-SAFT, used for technical evaluation, without relying on experimental data, often unavailable for such systems. The approach departs from the thermodynamic characterization of several pure-components, including novel fluorine-based refrigerants. The parametrization allows an excellent description of the vapor pressure, saturated densities, and latent heat. Next, a constant, temperature-independent binary parameter is used to estimate the solubility profiles of CO2-derived mixtures in selected refrigerants. The model effectively captures azeotropic and zeotropic behaviors, demonstrating its strength in fine-tuning solubility with minimal corrections. Subsequently, data from the molecular characterization via polar soft-SAFT is used as output targets to train a machine learning algorithm based on artificial neural networks, enabling the prediction of mixture saturation properties out of the training dataset's scope. Using COSMO σ-profiles, the developed ANN demonstrates high efficiency in predicting saturation bubble and dew temperatures, achieving R² > 0.9999, RMSE< 0.0959, AARD < 0.0220 %, and NMAD of 0.00044. Statistical analysis confirms minimal mean deviations, with outliers limited to 2.63 % for bubble and 2.44% for dew phase predictions, respectively.
{"title":"Machine learning integration in thermodynamics: Predicting CO2 mixture saturation properties for sustainable refrigeration applications","authors":"Carlos G. Albà ,&nbsp;Ismail I.I. Alkhatib ,&nbsp;Lourdes F. Vega ,&nbsp;Fèlix Llovell","doi":"10.1016/j.jcou.2025.103072","DOIUrl":"10.1016/j.jcou.2025.103072","url":null,"abstract":"<div><div>The need for sustainable alternatives in refrigeration has grown as Europe enforces mandates on avoiding high global warming potential (GWP) refrigerants. CO₂-based refrigerants have emerged as a promising choice in response, distinguished by its low GWP and reduced flammability, compared to formulated hydrofluoroolefins, thus offering a safer and sustainable solution in the context of next generation drop-in refrigerants. This study presents a machine-learning-based methodology to estimate the saturation properties of CO<sub>2</sub>-based mixtures, allowing for the precise tuning of molecular-based models like the polar soft-SAFT, used for technical evaluation, without relying on experimental data, often unavailable for such systems. The approach departs from the thermodynamic characterization of several pure-components, including novel fluorine-based refrigerants. The parametrization allows an excellent description of the vapor pressure, saturated densities, and latent heat. Next, a constant, temperature-independent binary parameter is used to estimate the solubility profiles of CO<sub>2</sub>-derived mixtures in selected refrigerants. The model effectively captures azeotropic and zeotropic behaviors, demonstrating its strength in fine-tuning solubility with minimal corrections. Subsequently, data from the molecular characterization via polar soft-SAFT is used as output targets to train a machine learning algorithm based on artificial neural networks, enabling the prediction of mixture saturation properties out of the training dataset's scope. Using COSMO σ-profiles, the developed ANN demonstrates high efficiency in predicting saturation bubble and dew temperatures, achieving R² &gt; 0.9999, RMSE&lt; 0.0959, AARD &lt; 0.0220 %, and NMAD of 0.00044. Statistical analysis confirms minimal mean deviations, with outliers limited to 2.63 % for bubble and 2.44% for dew phase predictions, respectively.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103072"},"PeriodicalIF":7.2,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photocatalytic and surface consequences of thermal treatments on Pt nanoparticles onto carbon nitrides during CO2-to-CO conversion 在二氧化碳转化为二氧化碳的过程中,对氮化碳上的铂纳米颗粒进行热处理的光催化效应和表面效应
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-29 DOI: 10.1016/j.jcou.2025.103068
S. Vaquero-Vílchez , P. Nimax , E. Valtierra-Martinez , I. Ayesta , I. Agirrezabal-Telleria
Photocatalysis is an emerging alternative to convert CO2 into relevant products, but it faces technological challenges related to charge recombination and low efficiency. Thermally coupled gas phase photocatalysis can address these issues by lowering reaction temperatures and improving process efficiency. This work demonstrates that defect engineering, combined with Pt impregnation at various metal dispersion and sizes, can enhance photocatalytic properties in g-C3N4 materials. Structural changes in g-C3N4 and Pt oxidation state modification, significantly impact CO productivity from CO2. This study investigates how thermal treatments in H2 affect defect and thus vacancy formation in g-C3N4. Materials with 2 wt% Pt2+ species generate C–N3 vacancies, while Pt0 species with the same content lead to both C–N3 and N–C3 vacancies– within g-C3N4. These differences exhibit distinct reaction trends under dark conditions or upon light irradiation. To further understand these effects, detailed XPS analyses clarify the impact of reaction conditions on the material after pretreatment and catalysis. The findings show that g-C3N4 materials can reform their C–Nbonds after electron excitation through light exposure, enhancing and stabilizing the reaction's productivity. As a result, CO productivities up to 1.1 mmol·gcat−1·h−1 are achieved. This work is expected to contribute to understanding the effect of thermal treatment on carbon nitrides, particularly regarding defect engineering, and more broadly, the effects of temperature in photocatalysis.
光催化是将二氧化碳转化为相关产品的一种新兴替代方法,但它面临着与电荷重组和低效率有关的技术挑战。热耦合气相光催化技术可以通过降低反应温度和提高工艺效率来解决这些问题。这项研究表明,缺陷工程与不同金属分散度和尺寸的铂浸渍相结合,可以增强 g-C3N4 材料的光催化性能。g-C3N4 的结构变化和铂氧化态的改变会显著影响二氧化碳的 CO 产率。本研究探讨了 H2 中的热处理如何影响 g-C3N4 中的缺陷和空位形成。含有 2 wt% Pt2+ 物种的材料会产生 C-N3 空位,而相同含量的 Pt0 物种则会在 g-C3N4 中产生 C-N3 和 N-C3 空位。这些差异在黑暗条件下或光照下表现出截然不同的反应趋势。为了进一步了解这些影响,详细的 XPS 分析阐明了预处理和催化后反应条件对材料的影响。研究结果表明,g-C3N4 材料在光照射下受到电子激发后,其 C-N 键可以发生重整,从而提高并稳定了反应的生产率。因此,一氧化碳的生产率可达 1.1 mmol-gcat-1-h-1。这项研究有望帮助人们了解热处理对碳氮化物的影响,特别是缺陷工程方面的影响,以及更广泛的光催化过程中温度的影响。
{"title":"Photocatalytic and surface consequences of thermal treatments on Pt nanoparticles onto carbon nitrides during CO2-to-CO conversion","authors":"S. Vaquero-Vílchez ,&nbsp;P. Nimax ,&nbsp;E. Valtierra-Martinez ,&nbsp;I. Ayesta ,&nbsp;I. Agirrezabal-Telleria","doi":"10.1016/j.jcou.2025.103068","DOIUrl":"10.1016/j.jcou.2025.103068","url":null,"abstract":"<div><div>Photocatalysis is an emerging alternative to convert CO<sub>2</sub> into relevant products, but it faces technological challenges related to charge recombination and low efficiency. Thermally coupled gas phase photocatalysis can address these issues by lowering reaction temperatures and improving process efficiency. This work demonstrates that defect engineering, combined with Pt impregnation at various metal dispersion and sizes, can enhance photocatalytic properties in g-C<sub>3</sub>N<sub>4</sub> materials. Structural changes in g-C<sub>3</sub>N<sub>4</sub> and Pt oxidation state modification, significantly impact CO productivity from CO<sub>2</sub>. This study investigates how thermal treatments in H<sub>2</sub> affect defect and thus vacancy formation in g-C<sub>3</sub>N<sub>4</sub>. Materials with 2 wt% Pt<sup>2</sup><sup>+</sup> species generate C–N<sub>3</sub> vacancies, while Pt<sup>0</sup> species with the same content lead to both C–N<sub>3</sub> and N–C<sub>3</sub> vacancies– within g-C<sub>3</sub>N<sub>4</sub>. These differences exhibit distinct reaction trends under dark conditions or upon light irradiation. To further understand these effects, detailed XPS analyses clarify the impact of reaction conditions on the material after pretreatment and catalysis. The findings show that g-C<sub>3</sub>N<sub>4</sub> materials can reform their C–Nbonds after electron excitation through light exposure, enhancing and stabilizing the reaction's productivity. As a result, CO productivities up to 1.1 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup> are achieved. This work is expected to contribute to understanding the effect of thermal treatment on carbon nitrides, particularly regarding defect engineering, and more broadly, the effects of temperature in photocatalysis.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103068"},"PeriodicalIF":7.2,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143735076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Elucidating operational drivers of CO2 transfer and utilization efficiency in photosynthetic algae cultivation systems
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-29 DOI: 10.1016/j.jcou.2025.103069
Mauro Lua , Everett Eustance , Arnav Deshpande , John McGowen , Lieve M.L. Laurens
While photosynthetic algae-based systems have shown promise for reducing the carbon footprint associated with biofuel and biochemical production due higher yields than terrestrial crops, there are challenges associated with CO2 delivery and utilization resulting from the chemical and physical environment experienced. Point-source CO2 delivery is a critical component of intensive algal cultivation, but a significant fraction of the CO2 sparged into the aqueous environment is lost. In this context, we review the theoretical considerations for deconvoluting carbon transfer efficiency (CTE) and carbon utilization efficiency (CUE), specifically in microalgal cultivation in response to changes in media formulation and alkalinity. We introduce an empirical and operational approach to increase the efficiency of CO2 transfer and ultimately prime algal cultures for photosynthetic carbon assimilation. We define operational boundaries for improving CUE under a neutral pH regime, with conditions that maintain high algal biomass productivity. Our work supports both the implementation of strategies for increasing CUE as well as provides a framework for monitoring inorganic and organic carbon balances in controlled aqueous systems. The integration of water chemistry in media formulation with dissolved inorganic carbon (DIC) and alkalinity are primary drivers of the inorganic carbon flux from a concentrated CO2 source towards an accessible carbon source for microalgae. We outline a systematic approach by leveraging control over carbon delivery, operational pH in the neutral pH regime, and alkalinity to match available DIC of the media with the demands of the algae to help optimize CTE and CUE. This control increases the feasibility of large-scale biotic CO2 capture in aqueous systems.
{"title":"Elucidating operational drivers of CO2 transfer and utilization efficiency in photosynthetic algae cultivation systems","authors":"Mauro Lua ,&nbsp;Everett Eustance ,&nbsp;Arnav Deshpande ,&nbsp;John McGowen ,&nbsp;Lieve M.L. Laurens","doi":"10.1016/j.jcou.2025.103069","DOIUrl":"10.1016/j.jcou.2025.103069","url":null,"abstract":"<div><div>While photosynthetic algae-based systems have shown promise for reducing the carbon footprint associated with biofuel and biochemical production due higher yields than terrestrial crops, there are challenges associated with CO<sub>2</sub> delivery and utilization resulting from the chemical and physical environment experienced. Point-source CO<sub>2</sub> delivery is a critical component of intensive algal cultivation, but a significant fraction of the CO<sub>2</sub> sparged into the aqueous environment is lost. In this context, we review the theoretical considerations for deconvoluting carbon transfer efficiency (CTE) and carbon utilization efficiency (CUE), specifically in microalgal cultivation in response to changes in media formulation and alkalinity. We introduce an empirical and operational approach to increase the efficiency of CO<sub>2</sub> transfer and ultimately prime algal cultures for photosynthetic carbon assimilation. We define operational boundaries for improving CUE under a neutral pH regime, with conditions that maintain high algal biomass productivity. Our work supports both the implementation of strategies for increasing CUE as well as provides a framework for monitoring inorganic and organic carbon balances in controlled aqueous systems. The integration of water chemistry in media formulation with dissolved inorganic carbon (DIC) and alkalinity are primary drivers of the inorganic carbon flux from a concentrated CO<sub>2</sub> source towards an accessible carbon source for microalgae. We outline a systematic approach by leveraging control over carbon delivery, operational pH in the neutral pH regime, and alkalinity to match available DIC of the media with the demands of the algae to help optimize CTE and CUE. This control increases the feasibility of large-scale biotic CO<sub>2</sub> capture in aqueous systems.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103069"},"PeriodicalIF":7.2,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143725081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Impact of particle breakage on the carbonation of argon oxygen decarburization slag - limitations and energy assessment
IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-28 DOI: 10.1016/j.jcou.2025.103073
Nina Miladinović , Luka Ceyssens , Giuseppe Granata , Tom Van Gerven
Disposing waste from the steel-making industry and the ongoing rise in global carbon dioxide emissions represent significant challenges to overcome. Carbonation of steel slags, the main waste material formed in steelmaking processes, is one of the possible solutions. In this research, three different kinds of mills are compared in order to most effectively approach the carbonation of argon oxygen decarburization (AOD) steel slag while simultaneously milled. Using breakage potential as a parameter for quantitative comparison, it is shown that the planetary ball mill is noticeably performing better than the vibratory mill and the McCrone mill – up to 39 % in terms of breakage of particles. The breakage potential correlates well with the carbonation rate at all three examined speeds (200 rpm, 500 rpm and 800 rpm) in the planetary ball mill. However, it is estimated that energy up to 120 kJ/g is used for the breakage of particles. Energy applied above this threshold contributes mainly to the agglomeration, but at different rates depending on the implemented speed. This difference is due to the varying contribution of two influencing parameters during simultaneous carbonation and milling - the presence of water and the number of collisions of the grinding balls with the AOD steel slag. The present work gives insights into the breakage of steel slag particles, their carbonation potential and limitations for achieving higher carbonation rates as well as predicted energy usage to obtain these processes.
{"title":"Impact of particle breakage on the carbonation of argon oxygen decarburization slag - limitations and energy assessment","authors":"Nina Miladinović ,&nbsp;Luka Ceyssens ,&nbsp;Giuseppe Granata ,&nbsp;Tom Van Gerven","doi":"10.1016/j.jcou.2025.103073","DOIUrl":"10.1016/j.jcou.2025.103073","url":null,"abstract":"<div><div>Disposing waste from the steel-making industry and the ongoing rise in global carbon dioxide emissions represent significant challenges to overcome. Carbonation of steel slags, the main waste material formed in steelmaking processes, is one of the possible solutions. In this research, three different kinds of mills are compared in order to most effectively approach the carbonation of argon oxygen decarburization (AOD) steel slag while simultaneously milled. Using breakage potential as a parameter for quantitative comparison, it is shown that the planetary ball mill is noticeably performing better than the vibratory mill and the McCrone mill – up to 39 % in terms of breakage of particles. The breakage potential correlates well with the carbonation rate at all three examined speeds (200 rpm, 500 rpm and 800 rpm) in the planetary ball mill. However, it is estimated that energy up to 120 kJ/g is used for the breakage of particles. Energy applied above this threshold contributes mainly to the agglomeration, but at different rates depending on the implemented speed. This difference is due to the varying contribution of two influencing parameters during simultaneous carbonation and milling - the presence of water and the number of collisions of the grinding balls with the AOD steel slag. The present work gives insights into the breakage of steel slag particles, their carbonation potential and limitations for achieving higher carbonation rates as well as predicted energy usage to obtain these processes.</div></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":"95 ","pages":"Article 103073"},"PeriodicalIF":7.2,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Journal of CO2 Utilization
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