Pub Date : 2026-01-26DOI: 10.1021/acssuschemeng.5c11948
Christophe Vos,Galahad O’Rourke,Dirk De Vos,Christophe Vos,Galahad O’Rourke,Dirk De Vos
The chemical recycling of chlorinated plastics is industrially challenging due to the release of corrosive HCl and char formation. In this work, a novel upcycling route for chlorinated plastics, including polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chlorinated polyethylene (CPE), is developed. When ZnCl2-catalyzed dehydrochlorination (DHC) is combined with tandem DHC-hydrogenation, using a homogeneous Ru hydrogenation catalyst and metal oxides as a HCl trap, each plastic type can be selectively converted into an unsaturated polyolefin (UPO), which can be chemically split via metathesis. By rational design of reaction conditions, CPE (25 or 35 m% Cl) as a model substrate, a PVDC–PVC copolymer (66 m% Cl) and PVC (57 m% Cl) were consecutively converted into partially and fully dechlorinated UPOs. Both of these UPO products contained −CH2–CH2–sequences and up to 11 double bonds per 100 carbons. They were chemically split into α,ω-dienes using a second-generation Grubbs catalyst. Via this procedure, chlorinated plastics can be converted into valuable chemical building blocks, while the released HCl is sequestered.
{"title":"Chemical Upcycling of Waste Chlorinated Plastics into α,ω-Dienes via Consecutive Dehydrochlorination-Hydrogenation with HCl Trapping and Metathesis","authors":"Christophe Vos,Galahad O’Rourke,Dirk De Vos,Christophe Vos,Galahad O’Rourke,Dirk De Vos","doi":"10.1021/acssuschemeng.5c11948","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11948","url":null,"abstract":"The chemical recycling of chlorinated plastics is industrially challenging due to the release of corrosive HCl and char formation. In this work, a novel upcycling route for chlorinated plastics, including polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chlorinated polyethylene (CPE), is developed. When ZnCl2-catalyzed dehydrochlorination (DHC) is combined with tandem DHC-hydrogenation, using a homogeneous Ru hydrogenation catalyst and metal oxides as a HCl trap, each plastic type can be selectively converted into an unsaturated polyolefin (UPO), which can be chemically split via metathesis. By rational design of reaction conditions, CPE (25 or 35 m% Cl) as a model substrate, a PVDC–PVC copolymer (66 m% Cl) and PVC (57 m% Cl) were consecutively converted into partially and fully dechlorinated UPOs. Both of these UPO products contained −CH2–CH2–sequences and up to 11 double bonds per 100 carbons. They were chemically split into α,ω-dienes using a second-generation Grubbs catalyst. Via this procedure, chlorinated plastics can be converted into valuable chemical building blocks, while the released HCl is sequestered.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"288 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
While anatase-TiO2/α-Fe2O3 (ATAF) composites are promising visible-light photocatalysts, their conventional synthesis is hindered by prolonged processing and high-temperature calcination, which limits scalability and increases energy consumption. This work demonstrates a rapid, single-step microwave-hydrothermal strategy to fabricate phase-pure ATAF composites within 10 min, entirely without calcination. This method facilitates the heterogeneous nucleation of anatase-TiO2 onto α-Fe2O3 particles, creating an intimate interface. By optimizing the α-Fe2O3 content with uniform TiO2 decoration on it, an ATAF composite exhibiting superior charge separation, as evidenced by significant photoluminescence quenching, is prepared. This optimal interface engineering results in a remarkable 99.9% photocatalytic degradation of methylene blue under visible light, significantly outperforming the individual constituents. This energy-efficient approach potentially reduces synthesis energy consumption by one to 2 orders of magnitude compared to conventional calcination routes, while the use of aqueous solvents and a closed system aligns with the principles of clean production. The combined advantages of rapid processing, energy efficiency, and scalability position this method as a viable pathway for the industrial-scale production of high-performance photocatalytic composites. The microwave-assisted hydrothermal synthesis demonstrates process electrification by transitioning from conventional furnace-based thermal treatment to direct microwave heating, resulting in reduced energy consumption and associated CO2 emissions.
{"title":"Microwave Electrification as a Process-Intensification Strategy for Calcination-Free, Scalable, and Sustainable Synthesis of Anatase-TiO2/α-Fe2O3 Photocatalysts","authors":"Praveen Kumar Lavudya,Sesha SuryaBindu Devarakonda,Dharani Kumar Chennamsetty,Nowduru Ravikiran,Venkata Satya Siva Srikanth Vadali,Rajanikanth Ammanabrolu","doi":"10.1021/acssuschemeng.5c12003","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12003","url":null,"abstract":"While anatase-TiO2/α-Fe2O3 (ATAF) composites are promising visible-light photocatalysts, their conventional synthesis is hindered by prolonged processing and high-temperature calcination, which limits scalability and increases energy consumption. This work demonstrates a rapid, single-step microwave-hydrothermal strategy to fabricate phase-pure ATAF composites within 10 min, entirely without calcination. This method facilitates the heterogeneous nucleation of anatase-TiO2 onto α-Fe2O3 particles, creating an intimate interface. By optimizing the α-Fe2O3 content with uniform TiO2 decoration on it, an ATAF composite exhibiting superior charge separation, as evidenced by significant photoluminescence quenching, is prepared. This optimal interface engineering results in a remarkable 99.9% photocatalytic degradation of methylene blue under visible light, significantly outperforming the individual constituents. This energy-efficient approach potentially reduces synthesis energy consumption by one to 2 orders of magnitude compared to conventional calcination routes, while the use of aqueous solvents and a closed system aligns with the principles of clean production. The combined advantages of rapid processing, energy efficiency, and scalability position this method as a viable pathway for the industrial-scale production of high-performance photocatalytic composites. The microwave-assisted hydrothermal synthesis demonstrates process electrification by transitioning from conventional furnace-based thermal treatment to direct microwave heating, resulting in reduced energy consumption and associated CO2 emissions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"51 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044929","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1021/acssuschemeng.5c11948
Christophe Vos,Galahad O’Rourke,Dirk De Vos
The chemical recycling of chlorinated plastics is industrially challenging due to the release of corrosive HCl and char formation. In this work, a novel upcycling route for chlorinated plastics, including polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chlorinated polyethylene (CPE), is developed. When ZnCl2-catalyzed dehydrochlorination (DHC) is combined with tandem DHC-hydrogenation, using a homogeneous Ru hydrogenation catalyst and metal oxides as a HCl trap, each plastic type can be selectively converted into an unsaturated polyolefin (UPO), which can be chemically split via metathesis. By rational design of reaction conditions, CPE (25 or 35 m% Cl) as a model substrate, a PVDC–PVC copolymer (66 m% Cl) and PVC (57 m% Cl) were consecutively converted into partially and fully dechlorinated UPOs. Both of these UPO products contained −CH2–CH2–sequences and up to 11 double bonds per 100 carbons. They were chemically split into α,ω-dienes using a second-generation Grubbs catalyst. Via this procedure, chlorinated plastics can be converted into valuable chemical building blocks, while the released HCl is sequestered.
{"title":"Chemical Upcycling of Waste Chlorinated Plastics into α,ω-Dienes via Consecutive Dehydrochlorination-Hydrogenation with HCl Trapping and Metathesis","authors":"Christophe Vos,Galahad O’Rourke,Dirk De Vos","doi":"10.1021/acssuschemeng.5c11948","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11948","url":null,"abstract":"The chemical recycling of chlorinated plastics is industrially challenging due to the release of corrosive HCl and char formation. In this work, a novel upcycling route for chlorinated plastics, including polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chlorinated polyethylene (CPE), is developed. When ZnCl2-catalyzed dehydrochlorination (DHC) is combined with tandem DHC-hydrogenation, using a homogeneous Ru hydrogenation catalyst and metal oxides as a HCl trap, each plastic type can be selectively converted into an unsaturated polyolefin (UPO), which can be chemically split via metathesis. By rational design of reaction conditions, CPE (25 or 35 m% Cl) as a model substrate, a PVDC–PVC copolymer (66 m% Cl) and PVC (57 m% Cl) were consecutively converted into partially and fully dechlorinated UPOs. Both of these UPO products contained −CH2–CH2–sequences and up to 11 double bonds per 100 carbons. They were chemically split into α,ω-dienes using a second-generation Grubbs catalyst. Via this procedure, chlorinated plastics can be converted into valuable chemical building blocks, while the released HCl is sequestered.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"40 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1021/acssuschemeng.5c09674
Jie Zhang, Xiaofan Wang, Yirong Wang, Yulong Yan, Sheng Zhang, Lin Peng, Menggang Li, Kechang Xie, Junjie Li
Coal washing plays a vital role in improving coal quality and reducing atmospheric pollutant emissions from coal combustion. However, the water footprint burdens caused by substantial freshwater consumption and wastewater discharge remain poorly understood. In this study, a comprehensive water footprint framework for coal washing was developed and used for a bottom-up analysis based on firsthand data from 2,367 coal washing plants across China in 2022. Compared with the scenario where coal was not washed, the national coal washing industry increases the water footprint by 7.38 Gm3, bringing the total water footprint of China’s coal supply chain to 27.68 Gm3, with gray water accounting for 90.9%. The water footprint intensities of commercial coal varied between 6.93 and 27.33 m3/t depending on the washing technologies, with a national average of 8.73 m3/t. Among the various technologies, jigging and jigging-based combined processes demonstrated relatively low water footprint intensities. From a production perspective, the spatial distribution of water footprint intensities in China exhibits a “high in the south and low in the north” pattern. However, an interprovincial transfer of 12.72 Gm3 of water footprint exacerbated the spatial mismatch between coal resources and water availability, owing to mismatches between production and consumption centers and prevailing trade flows. This study highlights the significant contribution of coal washing to the total water footprint of the coal life cycle and underscores the urgent need to incorporate water footprint balance into policies and decision-making regarding coal washing practices.
{"title":"Increased Giga-Cubic Meters of the Water Footprint of China’s Coal Caused by Washing","authors":"Jie Zhang, Xiaofan Wang, Yirong Wang, Yulong Yan, Sheng Zhang, Lin Peng, Menggang Li, Kechang Xie, Junjie Li","doi":"10.1021/acssuschemeng.5c09674","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09674","url":null,"abstract":"Coal washing plays a vital role in improving coal quality and reducing atmospheric pollutant emissions from coal combustion. However, the water footprint burdens caused by substantial freshwater consumption and wastewater discharge remain poorly understood. In this study, a comprehensive water footprint framework for coal washing was developed and used for a bottom-up analysis based on firsthand data from 2,367 coal washing plants across China in 2022. Compared with the scenario where coal was not washed, the national coal washing industry increases the water footprint by 7.38 Gm<sup>3</sup>, bringing the total water footprint of China’s coal supply chain to 27.68 Gm<sup>3</sup>, with gray water accounting for 90.9%. The water footprint intensities of commercial coal varied between 6.93 and 27.33 m<sup>3</sup>/t depending on the washing technologies, with a national average of 8.73 m<sup>3</sup>/t. Among the various technologies, jigging and jigging-based combined processes demonstrated relatively low water footprint intensities. From a production perspective, the spatial distribution of water footprint intensities in China exhibits a “high in the south and low in the north” pattern. However, an interprovincial transfer of 12.72 Gm<sup>3</sup> of water footprint exacerbated the spatial mismatch between coal resources and water availability, owing to mismatches between production and consumption centers and prevailing trade flows. This study highlights the significant contribution of coal washing to the total water footprint of the coal life cycle and underscores the urgent need to incorporate water footprint balance into policies and decision-making regarding coal washing practices.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
While anatase-TiO2/α-Fe2O3 (ATAF) composites are promising visible-light photocatalysts, their conventional synthesis is hindered by prolonged processing and high-temperature calcination, which limits scalability and increases energy consumption. This work demonstrates a rapid, single-step microwave-hydrothermal strategy to fabricate phase-pure ATAF composites within 10 min, entirely without calcination. This method facilitates the heterogeneous nucleation of anatase-TiO2 onto α-Fe2O3 particles, creating an intimate interface. By optimizing the α-Fe2O3 content with uniform TiO2 decoration on it, an ATAF composite exhibiting superior charge separation, as evidenced by significant photoluminescence quenching, is prepared. This optimal interface engineering results in a remarkable 99.9% photocatalytic degradation of methylene blue under visible light, significantly outperforming the individual constituents. This energy-efficient approach potentially reduces synthesis energy consumption by one to 2 orders of magnitude compared to conventional calcination routes, while the use of aqueous solvents and a closed system aligns with the principles of clean production. The combined advantages of rapid processing, energy efficiency, and scalability position this method as a viable pathway for the industrial-scale production of high-performance photocatalytic composites. The microwave-assisted hydrothermal synthesis demonstrates process electrification by transitioning from conventional furnace-based thermal treatment to direct microwave heating, resulting in reduced energy consumption and associated CO2 emissions.
{"title":"Microwave Electrification as a Process-Intensification Strategy for Calcination-Free, Scalable, and Sustainable Synthesis of Anatase-TiO2/α-Fe2O3 Photocatalysts","authors":"Praveen Kumar Lavudya,Sesha SuryaBindu Devarakonda,Dharani Kumar Chennamsetty,Nowduru Ravikiran,Venkata Satya Siva Srikanth Vadali,Rajanikanth Ammanabrolu","doi":"10.1021/acssuschemeng.5c12003","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12003","url":null,"abstract":"While anatase-TiO2/α-Fe2O3 (ATAF) composites are promising visible-light photocatalysts, their conventional synthesis is hindered by prolonged processing and high-temperature calcination, which limits scalability and increases energy consumption. This work demonstrates a rapid, single-step microwave-hydrothermal strategy to fabricate phase-pure ATAF composites within 10 min, entirely without calcination. This method facilitates the heterogeneous nucleation of anatase-TiO2 onto α-Fe2O3 particles, creating an intimate interface. By optimizing the α-Fe2O3 content with uniform TiO2 decoration on it, an ATAF composite exhibiting superior charge separation, as evidenced by significant photoluminescence quenching, is prepared. This optimal interface engineering results in a remarkable 99.9% photocatalytic degradation of methylene blue under visible light, significantly outperforming the individual constituents. This energy-efficient approach potentially reduces synthesis energy consumption by one to 2 orders of magnitude compared to conventional calcination routes, while the use of aqueous solvents and a closed system aligns with the principles of clean production. The combined advantages of rapid processing, energy efficiency, and scalability position this method as a viable pathway for the industrial-scale production of high-performance photocatalytic composites. The microwave-assisted hydrothermal synthesis demonstrates process electrification by transitioning from conventional furnace-based thermal treatment to direct microwave heating, resulting in reduced energy consumption and associated CO2 emissions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
While anatase-TiO2/α-Fe2O3 (ATAF) composites are promising visible-light photocatalysts, their conventional synthesis is hindered by prolonged processing and high-temperature calcination, which limits scalability and increases energy consumption. This work demonstrates a rapid, single-step microwave-hydrothermal strategy to fabricate phase-pure ATAF composites within 10 min, entirely without calcination. This method facilitates the heterogeneous nucleation of anatase-TiO2 onto α-Fe2O3 particles, creating an intimate interface. By optimizing the α-Fe2O3 content with uniform TiO2 decoration on it, an ATAF composite exhibiting superior charge separation, as evidenced by significant photoluminescence quenching, is prepared. This optimal interface engineering results in a remarkable 99.9% photocatalytic degradation of methylene blue under visible light, significantly outperforming the individual constituents. This energy-efficient approach potentially reduces synthesis energy consumption by one to 2 orders of magnitude compared to conventional calcination routes, while the use of aqueous solvents and a closed system aligns with the principles of clean production. The combined advantages of rapid processing, energy efficiency, and scalability position this method as a viable pathway for the industrial-scale production of high-performance photocatalytic composites. The microwave-assisted hydrothermal synthesis demonstrates process electrification by transitioning from conventional furnace-based thermal treatment to direct microwave heating, resulting in reduced energy consumption and associated CO2 emissions.
{"title":"Microwave Electrification as a Process-Intensification Strategy for Calcination-Free, Scalable, and Sustainable Synthesis of Anatase-TiO2/α-Fe2O3 Photocatalysts","authors":"Praveen Kumar Lavudya,Sesha SuryaBindu Devarakonda,Dharani Kumar Chennamsetty,Nowduru Ravikiran,Venkata Satya Siva Srikanth Vadali,Rajanikanth Ammanabrolu,Praveen Kumar Lavudya,Sesha SuryaBindu Devarakonda,Dharani Kumar Chennamsetty,Nowduru Ravikiran,Venkata Satya Siva Srikanth Vadali,Rajanikanth Ammanabrolu,Praveen Kumar Lavudya,Sesha SuryaBindu Devarakonda,Dharani Kumar Chennamsetty,Nowduru Ravikiran,Venkata Satya Siva Srikanth Vadali,Rajanikanth Ammanabrolu","doi":"10.1021/acssuschemeng.5c12003","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12003","url":null,"abstract":"While anatase-TiO2/α-Fe2O3 (ATAF) composites are promising visible-light photocatalysts, their conventional synthesis is hindered by prolonged processing and high-temperature calcination, which limits scalability and increases energy consumption. This work demonstrates a rapid, single-step microwave-hydrothermal strategy to fabricate phase-pure ATAF composites within 10 min, entirely without calcination. This method facilitates the heterogeneous nucleation of anatase-TiO2 onto α-Fe2O3 particles, creating an intimate interface. By optimizing the α-Fe2O3 content with uniform TiO2 decoration on it, an ATAF composite exhibiting superior charge separation, as evidenced by significant photoluminescence quenching, is prepared. This optimal interface engineering results in a remarkable 99.9% photocatalytic degradation of methylene blue under visible light, significantly outperforming the individual constituents. This energy-efficient approach potentially reduces synthesis energy consumption by one to 2 orders of magnitude compared to conventional calcination routes, while the use of aqueous solvents and a closed system aligns with the principles of clean production. The combined advantages of rapid processing, energy efficiency, and scalability position this method as a viable pathway for the industrial-scale production of high-performance photocatalytic composites. The microwave-assisted hydrothermal synthesis demonstrates process electrification by transitioning from conventional furnace-based thermal treatment to direct microwave heating, resulting in reduced energy consumption and associated CO2 emissions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The hydrogenation of CO2 to methanol serves as a practical approach extensively applied in achieving carbon cycling utilization and reducing carbon emissions. Nevertheless, the rational design of Cu-based catalysts with satisfactory catalytic performance and corresponding structure–activity relationship understanding still remains a challenging goal. Inspired by the characteristics of both hydrotalcite structures and active Cu species for CO2 hydrogenation, a series of hydrotalcite-derived Cu nanocatalysts with highly dispersed Cu nanoclusters and tunable electronic and geometric structures are obtained via simply controlling structural topological transformation process temperature, verified by a comprehensive study including Bader charge analyses, TG-MS, HAADF-STEM, in situ CO–DRIFTS, and XAFS experiments. The optimized catalyst demonstrates an exceptional normalized CO2 reaction rate of 30.6 mmol·gcat–1·h–1 and a methanol selectivity of 92%, yielding an excellent methanol space-time yield (∼0.9 g·gcat–1·h–1) and a stability of 100 h under mild conditions (220 °C, 3 MPa). This is approximately twice that of the control catalyst and ranks among the top outcomes reported so far for Cu-based systems. Operando FTIR, structure–activity relationship, and DFT studies elucidate that the active Cu species at the Cu–ZnO interface function as intrinsic active centers, accelerating the formation of key intermediates (HCOO* and H3CO*), leading to a lower activation-energy barrier. Therefore, this work presents an effective strategy for fabricating Cu nanocatalysts featuring a precisely controllable Cu–ZnO interface via a facile LDH topological transformation, offering a promising application path in the large-scale synthesis of methanol from CO2 hydrogenation.
{"title":"Enhancing CO2 Hydrogenation to Methanol at Tunable Cu–ZnO Interfaces on Hydrotalcite-Derived Cu Nanocatalysts","authors":"Guoqing Cui, Yingjie Lou, Yiyang Hu, Mingxia Zhou, Yuming Li, Yajun Wang, Wei Wang, Jiong Li, Guiyuan Jiang, Chunming Xu","doi":"10.1021/acssuschemeng.5c10863","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10863","url":null,"abstract":"The hydrogenation of CO<sub>2</sub> to methanol serves as a practical approach extensively applied in achieving carbon cycling utilization and reducing carbon emissions. Nevertheless, the rational design of Cu-based catalysts with satisfactory catalytic performance and corresponding structure–activity relationship understanding still remains a challenging goal. Inspired by the characteristics of both hydrotalcite structures and active Cu species for CO<sub>2</sub> hydrogenation, a series of hydrotalcite-derived Cu nanocatalysts with highly dispersed Cu nanoclusters and tunable electronic and geometric structures are obtained via simply controlling structural topological transformation process temperature, verified by a comprehensive study including Bader charge analyses, TG-MS, HAADF-STEM, <i>in situ</i> CO–DRIFTS, and XAFS experiments. The optimized catalyst demonstrates an exceptional normalized CO<sub>2</sub> reaction rate of 30.6 mmol·g<sub>cat</sub><sup>–1</sup>·h<sup>–1</sup> and a methanol selectivity of 92%, yielding an excellent methanol space-time yield (∼0.9 g·g<sub>cat</sub><sup>–1</sup>·h<sup>–1</sup>) and a stability of 100 h under mild conditions (220 °C, 3 MPa). This is approximately twice that of the control catalyst and ranks among the top outcomes reported so far for Cu-based systems. <i>Operando</i> FTIR, structure–activity relationship, and DFT studies elucidate that the active Cu species at the Cu–ZnO interface function as intrinsic active centers, accelerating the formation of key intermediates (HCOO* and H<sub>3</sub>CO*), leading to a lower activation-energy barrier. Therefore, this work presents an effective strategy for fabricating Cu nanocatalysts featuring a precisely controllable Cu–ZnO interface via a facile LDH topological transformation, offering a promising application path in the large-scale synthesis of methanol from CO<sub>2</sub> hydrogenation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044925","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-25DOI: 10.1021/acssuschemeng.5c11507
Kexin Zhou, Zihan Zhang, Junqi Gao, Bingqiang Pan, Kexia Jin, Yuxuan Xia, Da Zhang, Hongkun Wang, Yang Zhu, Wen-Jun Wang, Xuan Yang
The transition toward sustainable plastics calls for biodegradable polymers with enhanced performance and scalable processing routes. Plant-derived nanofibers are promising reinforcements, yet their adoption is hindered by energy-intensive isolation, incompatibility with hydrophobic matrices, and aggregation during drying. Here, we report a dual-function reactive extrusion strategy that combines nanofibrillation and surface modification in a single step. Lignocellulosic fibers are prefunctionalized with maleic anhydride to introduce carboxyl groups while retaining native lignin, and in-situ transesterification during melt compounding generates well-dispersed cellulose nanofibrils covalently bonded to PBAT. This integrated approach removes the need for costly nanocellulose isolation and drying while simultaneously ensuring compatibility and mechanical integrity through both chemical bonding and the hydrophobic contribution of lignin. The resulting composite films exhibit a 30% increase in stiffness while maintaining superior tensile strength and strain at failure, along with a 42% and 56% reduction in water vapor and oxygen permeability, respectively, compared to neat polymers. Additionally, the preserved lignin imparts over 90% antibacterial activity, enabling improved fruit preservation, while many film trials confirmed effective soil moisture retention and good biodegradability. Overall, this work establishes a scalable, industry-ready route to transform raw biomass into multifunctional nanofillers, providing a green pathway toward high-performance composite films for packaging and agricultural applications.
{"title":"Dual-Function Reactive Extrusion of Lignocellulosic Fibers for High-Performance Biodegradable Nanocomposite Films","authors":"Kexin Zhou, Zihan Zhang, Junqi Gao, Bingqiang Pan, Kexia Jin, Yuxuan Xia, Da Zhang, Hongkun Wang, Yang Zhu, Wen-Jun Wang, Xuan Yang","doi":"10.1021/acssuschemeng.5c11507","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11507","url":null,"abstract":"The transition toward sustainable plastics calls for biodegradable polymers with enhanced performance and scalable processing routes. Plant-derived nanofibers are promising reinforcements, yet their adoption is hindered by energy-intensive isolation, incompatibility with hydrophobic matrices, and aggregation during drying. Here, we report a dual-function reactive extrusion strategy that combines nanofibrillation and surface modification in a single step. Lignocellulosic fibers are prefunctionalized with maleic anhydride to introduce carboxyl groups while retaining native lignin, and <i>in-situ</i> transesterification during melt compounding generates well-dispersed cellulose nanofibrils covalently bonded to PBAT. This integrated approach removes the need for costly nanocellulose isolation and drying while simultaneously ensuring compatibility and mechanical integrity through both chemical bonding and the hydrophobic contribution of lignin. The resulting composite films exhibit a 30% increase in stiffness while maintaining superior tensile strength and strain at failure, along with a 42% and 56% reduction in water vapor and oxygen permeability, respectively, compared to neat polymers. Additionally, the preserved lignin imparts over 90% antibacterial activity, enabling improved fruit preservation, while many film trials confirmed effective soil moisture retention and good biodegradability. Overall, this work establishes a scalable, industry-ready route to transform raw biomass into multifunctional nanofillers, providing a green pathway toward high-performance composite films for packaging and agricultural applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"44 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-24DOI: 10.1021/acssuschemeng.5c11668
Kailun Chen, Li Lin, Jinglin Li, Endian Hu, Jingwen Chang, Ke Liu, Jianguo Jiang
Washing and thermal treatment are among the most promising technologies for managing municipal solid waste incineration fly ash (FA). However, the fate of residual ash after treatment remains uncertain and requires further investigation to achieve full resource utilization. In this study, the feasibility of using raw fly ash (RFA), washed fly ash (WFA), and thermally activated fly ash (TFA) as partial replacements for cement in composite cementitious materials was investigated. The macroscopic properties, strength development, environmental safety, and hydration mechanisms of FA-based composites were systematically examined. After the removal of hazardous substances, the physicochemical properties of WFA and TFA became closer to those of ordinary Portland cement (OPC). The mechanical performance of the composites followed the order TFA > WFA > RFA. At a 30% replacement level, the compressive strength of TFA reached 64.2 MPa, slightly higher than that of pure OPC and 103% greater than that of RFA. The corresponding carbon emission calibrated by strength is 29.5% lower than that of pure OPC, reaching 672.5 kgCO2e/t. In terms of environmental performance, heavy-metal leaching from all FA-based composites met the relevant standards, and the chloride immobilization efficiency exceeded 90%. The crystalline phases of hydration products included ettringite (AFt), calcium silicate hydrate [C-(A)-S-H], and Friedel’s salt. During hydration, the formation of portlandite, precipitation of AFt, and deposition of C-(A)-S-H led to an interlaced microstructure in the TFA-derived composites, effectively refining the microstructure and thereby enhancing the macroscopic performance. These findings provide a reference pathway for the utilization of FA and contribute to the sustainable management of FA.
洗涤和热处理是处理城市固体垃圾焚烧飞灰最有前途的技术。然而，处理后的残灰的命运仍然不确定，需要进一步研究，以实现充分的资源利用。在本研究中，研究了在复合胶凝材料中使用生粉煤灰（RFA）、水洗粉煤灰（WFA）和热活化粉煤灰（TFA）部分替代水泥的可行性。系统地研究了fa基复合材料的宏观性能、强度发展、环境安全性和水化机理。在去除有害物质后，WFA和TFA的物理化学性能更接近于普通硅酸盐水泥（OPC）。复合材料的力学性能表现为TFA >； WFA >； RFA。在30%替代水平下，TFA的抗压强度达到64.2 MPa，略高于纯OPC，比RFA高103%。与纯OPC相比，强度标定的碳排放量降低了29.5%，达到672.5 kgCO2e/t。在环保性能方面，fa基复合材料重金属浸出均达到相关标准，氯离子固定化效率超过90%。水化产物的晶相包括钙矾石（AFt）、水合硅酸钙[C-(A)- s - h]和弗里德尔盐。水化过程中，硅酸盐的形成、AFt的沉淀和C-(A)- s - h的沉积导致tfa衍生复合材料的微观结构呈交错状，有效地细化了微观结构，从而提高了宏观性能。研究结果为农用植物资源的利用提供了参考途径，有助于农用植物资源的可持续管理。
{"title":"Boosted Performance of Composite Cementitious Materials Derived from Incineration Fly Ash via Thermal Activation","authors":"Kailun Chen, Li Lin, Jinglin Li, Endian Hu, Jingwen Chang, Ke Liu, Jianguo Jiang","doi":"10.1021/acssuschemeng.5c11668","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11668","url":null,"abstract":"Washing and thermal treatment are among the most promising technologies for managing municipal solid waste incineration fly ash (FA). However, the fate of residual ash after treatment remains uncertain and requires further investigation to achieve full resource utilization. In this study, the feasibility of using raw fly ash (RFA), washed fly ash (WFA), and thermally activated fly ash (TFA) as partial replacements for cement in composite cementitious materials was investigated. The macroscopic properties, strength development, environmental safety, and hydration mechanisms of FA-based composites were systematically examined. After the removal of hazardous substances, the physicochemical properties of WFA and TFA became closer to those of ordinary Portland cement (OPC). The mechanical performance of the composites followed the order TFA > WFA > RFA. At a 30% replacement level, the compressive strength of TFA reached 64.2 MPa, slightly higher than that of pure OPC and 103% greater than that of RFA. The corresponding carbon emission calibrated by strength is 29.5% lower than that of pure OPC, reaching 672.5 kgCO<sub>2</sub>e/t. In terms of environmental performance, heavy-metal leaching from all FA-based composites met the relevant standards, and the chloride immobilization efficiency exceeded 90%. The crystalline phases of hydration products included ettringite (AFt), calcium silicate hydrate [C-(A)-S-H], and Friedel’s salt. During hydration, the formation of portlandite, precipitation of AFt, and deposition of C-(A)-S-H led to an interlaced microstructure in the TFA-derived composites, effectively refining the microstructure and thereby enhancing the macroscopic performance. These findings provide a reference pathway for the utilization of FA and contribute to the sustainable management of FA.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"186 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1021/acssuschemeng.5c06535
Yijuan Chang, Enwen Liu, haiqiao Zhang, Zhihui Wu
This study reports the development of a dual self-healing, antibacterial, and pH-responsive wood coating using intelligent microcapsule technology. Microcapsules were synthesized with UV wood wax oil (UVW) as the core and hydroxypropyl methylcellulose/TiO2-modified chitosan as the shell, achieving 78.2% encapsulation efficiency. The microcapsules released contents most effectively in a pH 9 water, sustaining release for 1000 h following Fickian diffusion. The coating with 10.0% microcapsules reached a healing efficiency of 83.3% after 8 days at room temperature, while 2.0% microcapsule coatings achieved 42.9% healing under 10 min UV exposure. The 2.0% coating also demonstrated antibacterial activity against Escherichia coli (E. coli) at 75.82%. In addition, it showed minimal yellowing, gloss loss, and color change under cold liquid exposure. The coating exhibited strong mechanical performance, with a load-bearing capacity of 129.363 N, adhesion strength of 8.985 MPa, and maximum elongation at break of 8.87%. These results support the potential of this multifunctional coating for advanced wood surface protection.
{"title":"Construction of Chitosan Microcapsules Using Ultraviolet Wood Wax Oil for Self-Healing Antibacterial Wood Coatings","authors":"Yijuan Chang, Enwen Liu, haiqiao Zhang, Zhihui Wu","doi":"10.1021/acssuschemeng.5c06535","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c06535","url":null,"abstract":"This study reports the development of a dual self-healing, antibacterial, and pH-responsive wood coating using intelligent microcapsule technology. Microcapsules were synthesized with UV wood wax oil (UVW) as the core and hydroxypropyl methylcellulose/TiO<sub>2</sub>-modified chitosan as the shell, achieving 78.2% encapsulation efficiency. The microcapsules released contents most effectively in a pH 9 water, sustaining release for 1000 h following Fickian diffusion. The coating with 10.0% microcapsules reached a healing efficiency of 83.3% after 8 days at room temperature, while 2.0% microcapsule coatings achieved 42.9% healing under 10 min UV exposure. The 2.0% coating also demonstrated antibacterial activity against <i><i>Escherichia coli</i></i> (<i><i>E. coli</i></i>) at 75.82%. In addition, it showed minimal yellowing, gloss loss, and color change under cold liquid exposure. The coating exhibited strong mechanical performance, with a load-bearing capacity of 129.363 N, adhesion strength of 8.985 MPa, and maximum elongation at break of 8.87%. These results support the potential of this multifunctional coating for advanced wood surface protection.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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