Pub Date : 2026-01-29DOI: 10.1021/acssuschemeng.5c07641
Gijs J. A. Brouwer, , , Tamara Janković, , , John A. Posada, , , Adrie J. J. Straathof, , and , Anton A. Kiss*,
This study advances the development of syngas fermentation by presenting the first industrial-scale process design for producing isopropanol (IPA) and acetone from steel mill off-gas, with a total production capacity of 46–50 ktonne per year. The process was rigorously developed in Aspen Plus, with a comprehensive techno-economic assessment and life-cycle analysis performed to evaluate the process performance. The developed process maximizes energy efficiency by utilizing the heat content of steel off-gas and implementing advanced heat pump systems. As a result, the process is thermally self-sufficient and can operate solely on renewable electricity. Efficient utilization of waste gases results in substantial reductions in global warming potential compared with petrochemical-based production (144–160% for IPA and 138–149% for acetone). The unit production cost of 0.58–0.74 $/kgIPA/Ac and potential profit margins of 49–65% testify to the cost-effectiveness of the developed process. These findings demonstrate the environmental and economic sustainability of syngas fermentation from steel mill off-gas, establishing it as a potentially viable alternative to conventional petrochemical processes. This technology may hold great potential in reducing environmental impacts and carbon emissions in industrial chemical production.
{"title":"Thermally Self-Sufficient Process for Sustainable Production of Isopropanol and Acetone via Syngas Fermentation","authors":"Gijs J. A. Brouwer, , , Tamara Janković, , , John A. Posada, , , Adrie J. J. Straathof, , and , Anton A. Kiss*, ","doi":"10.1021/acssuschemeng.5c07641","DOIUrl":"10.1021/acssuschemeng.5c07641","url":null,"abstract":"<p >This study advances the development of syngas fermentation by presenting the first industrial-scale process design for producing isopropanol (IPA) and acetone from steel mill off-gas, with a total production capacity of 46–50 ktonne per year. The process was rigorously developed in Aspen Plus, with a comprehensive techno-economic assessment and life-cycle analysis performed to evaluate the process performance. The developed process maximizes energy efficiency by utilizing the heat content of steel off-gas and implementing advanced heat pump systems. As a result, the process is thermally self-sufficient and can operate solely on renewable electricity. Efficient utilization of waste gases results in substantial reductions in global warming potential compared with petrochemical-based production (144–160% for IPA and 138–149% for acetone). The unit production cost of 0.58–0.74 $/kg<sub>IPA/Ac</sub> and potential profit margins of 49–65% testify to the cost-effectiveness of the developed process. These findings demonstrate the environmental and economic sustainability of syngas fermentation from steel mill off-gas, establishing it as a potentially viable alternative to conventional petrochemical processes. This technology may hold great potential in reducing environmental impacts and carbon emissions in industrial chemical production.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2318–2328"},"PeriodicalIF":7.3,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070148","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 : 2026-01-29DOI: 10.1021/acssuschemeng.5c11689
Valeria De Fabritiis, , , Leonardo Matta, , , Gianmarco Griffini*, , and , Stefano Turri*,
The use of carbon-fiber reinforced thermoset polymers (CFRPs) is continuously growing in a wide range of manufacturing sectors, particularly when high performance, lightweight design, and corrosion resistance are required. However, their multimaterial cross-linked structure hinders their recyclability, resulting in the extensive generation of heterogeneous wastes. Nowadays, the correct management of end-of-life (EoL) thermosetting composites remains an open and unsolved issue. In this respect, this work presents a chemical recycling process of a model CFRP from an epoxy-amine network, operated at atmospheric pressure, relatively low temperature (≤200 °C), and mild pH (4–5), allowed by the modification of a Lewis acid catalyst. This process leads to complete liberation of the reinforcing carbon fibers without dimensional alteration, with mechanical characteristics fully comparable to the corresponding virgin fibers, and with the formation of a reusable oligomeric fraction. The recovered components are successfully upcycled by fabricating second-generation CFRPs. Finally, the solvolysis process is validated on real EoL composite parts from aerospace and sports equipment products. This work proposes an economically feasible, safe, and scalable approach to efficiently recycle amine-cured epoxy-based CFRPs, with reusability of all fractions and minimization of any secondary waste generation.
{"title":"Making Carbon-Fiber Reinforced Epoxy-Amine Thermoset Composites More Circular through Chemical Recycling by Catalyzed Solvolysis","authors":"Valeria De Fabritiis, , , Leonardo Matta, , , Gianmarco Griffini*, , and , Stefano Turri*, ","doi":"10.1021/acssuschemeng.5c11689","DOIUrl":"10.1021/acssuschemeng.5c11689","url":null,"abstract":"<p >The use of carbon-fiber reinforced thermoset polymers (CFRPs) is continuously growing in a wide range of manufacturing sectors, particularly when high performance, lightweight design, and corrosion resistance are required. However, their multimaterial cross-linked structure hinders their recyclability, resulting in the extensive generation of heterogeneous wastes. Nowadays, the correct management of end-of-life (EoL) thermosetting composites remains an open and unsolved issue. In this respect, this work presents a chemical recycling process of a model CFRP from an epoxy-amine network, operated at atmospheric pressure, relatively low temperature (≤200 °C), and mild pH (4–5), allowed by the modification of a Lewis acid catalyst. This process leads to complete liberation of the reinforcing carbon fibers without dimensional alteration, with mechanical characteristics fully comparable to the corresponding virgin fibers, and with the formation of a reusable oligomeric fraction. The recovered components are successfully upcycled by fabricating second-generation CFRPs. Finally, the solvolysis process is validated on real EoL composite parts from aerospace and sports equipment products. This work proposes an economically feasible, safe, and scalable approach to efficiently recycle amine-cured epoxy-based CFRPs, with reusability of all fractions and minimization of any secondary waste generation.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2546–2555"},"PeriodicalIF":7.3,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acssuschemeng.5c11689","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Crystallization is a key process in the chemical industry for manufacturing, separation, and purification. However, precise control over the crystal properties remains challenging. Ultrasound-assisted crystallization has been widely used to overcome these issues, but its continuous use can cause thermal degradation, reactor corrosion, and high energy consumption, limiting industrial scalability. Nanobubbles offer a green, sustainable alternative due to their high surface-to-volume ratio and strong negative surface charge, which promote nucleation and control crystal growth. This study compares ultrasound and nanobubbles in cooling crystallization. A theoretical analysis using a modified Gibbs free-energy equation showed that increased nanobubble surface charge reduces nucleation energy barriers by providing a relation of . Experimentally, nanobubbles shortened induction times, increased yield, and reduced crystal size from 171 to 83 μm. The variation in operating parameters for nanobubble production resulted in optimum conditions for crystallization. Overall, nanobubbles present a viable, non-invasive alternative to ultrasound, offering effective crystallization control without significant energy input, making them suitable for industrial-scale applications.
{"title":"Advancing Nanobubble-Assisted Crystallization as a Green and Sustainable Technology","authors":"Aakriti Sharma, , , Taranpreet Kaur, , and , Neelkanth Nirmalkar*, ","doi":"10.1021/acssuschemeng.5c09013","DOIUrl":"10.1021/acssuschemeng.5c09013","url":null,"abstract":"<p >Crystallization is a key process in the chemical industry for manufacturing, separation, and purification. However, precise control over the crystal properties remains challenging. Ultrasound-assisted crystallization has been widely used to overcome these issues, but its continuous use can cause thermal degradation, reactor corrosion, and high energy consumption, limiting industrial scalability. Nanobubbles offer a green, sustainable alternative due to their high surface-to-volume ratio and strong negative surface charge, which promote nucleation and control crystal growth. This study compares ultrasound and nanobubbles in cooling crystallization. A theoretical analysis using a modified Gibbs free-energy equation showed that increased nanobubble surface charge reduces nucleation energy barriers by providing a relation of <i></i><math><mfrac><mrow><mi>Δ</mi><mi>G</mi></mrow><mrow><msub><mi>k</mi><mi>B</mi></msub><mi>T</mi></mrow></mfrac><mo>∝</mo><mfrac><mi>Q</mi><msup><mi>r</mi><mo>*</mo></msup></mfrac></math>. Experimentally, nanobubbles shortened induction times, increased yield, and reduced crystal size from 171 to 83 μm. The variation in operating parameters for nanobubble production resulted in optimum conditions for crystallization. Overall, nanobubbles present a viable, non-invasive alternative to ultrasound, offering effective crystallization control without significant energy input, making them suitable for industrial-scale applications.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2339–2358"},"PeriodicalIF":7.3,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070149","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 : 2026-01-29DOI: 10.1021/acssuschemeng.5c11873
Jingxuan Lu, , , Qi Wang, , , Quan Wang*, , , Lei Yu, , , Rongping Chen, , and , Yi Wang,
Efficient extraction of biomolecules from high-moisture microalgae is constrained by the polarity mismatch between solvents and water. This study introduces a COSMO-RS-assisted computational–experimental framework for entrainer screening and mechanistic elucidation in subcritical dimethyl ether (DME)–water systems. A database of 1982 solvents was sequentially filtered by melting/boiling points, environmental, health, and safety (EHS) criteria, and COSMO-RS-predicted solubilities, followed by ternary-miscibility evaluation and targeted experiments. The integrated results reveal that extraction efficiency is primarily governed by ternary miscibility, with class-specific entrainers optimizing recovery across lipids, proteins, carbohydrates, and pigments. Excess-enthalpy (HE) decomposition identifies hydrogen bonding as the principal favorable contribution, opposed by electrostatic misfit. Electrostatic potential (ESP), independent gradient model based on Hirshfeld partition (IGMH), and interaction region indicator (IRI) analyses clarify how selected entrainers increase DME–water miscibility and enhance solvation of representative biomolecules. The framework offers predictive guidance for designing efficient, selective, and environmentally sustainable extraction processes for wet biomass valorization.
{"title":"Mechanism-Informed Computational Entrainer Selection and Process Design for Biomolecule Extraction from Primary-Concentrated Microalgae in Subcritical Dimethyl Ether Systems","authors":"Jingxuan Lu, , , Qi Wang, , , Quan Wang*, , , Lei Yu, , , Rongping Chen, , and , Yi Wang, ","doi":"10.1021/acssuschemeng.5c11873","DOIUrl":"10.1021/acssuschemeng.5c11873","url":null,"abstract":"<p >Efficient extraction of biomolecules from high-moisture microalgae is constrained by the polarity mismatch between solvents and water. This study introduces a COSMO-RS-assisted computational–experimental framework for entrainer screening and mechanistic elucidation in subcritical dimethyl ether (DME)–water systems. A database of 1982 solvents was sequentially filtered by melting/boiling points, environmental, health, and safety (EHS) criteria, and COSMO-RS-predicted solubilities, followed by ternary-miscibility evaluation and targeted experiments. The integrated results reveal that extraction efficiency is primarily governed by ternary miscibility, with class-specific entrainers optimizing recovery across lipids, proteins, carbohydrates, and pigments. Excess-enthalpy (H<sup>E</sup>) decomposition identifies hydrogen bonding as the principal favorable contribution, opposed by electrostatic misfit. Electrostatic potential (ESP), independent gradient model based on Hirshfeld partition (IGMH), and interaction region indicator (IRI) analyses clarify how selected entrainers increase DME–water miscibility and enhance solvation of representative biomolecules. The framework offers predictive guidance for designing efficient, selective, and environmentally sustainable extraction processes for wet biomass valorization.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2570–2582"},"PeriodicalIF":7.3,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070153","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 : 2026-01-29DOI: 10.1021/acssuschemeng.5c11399
An Huang, Yanjun Wan, Xianheng Song, Wenmei Feng, Shuyun Ju, Yajun Wang
Chiral β-cyano ester scaffolds are highly valuable synthons in pharmaceutical synthesis. The direct asymmetric hydrogenation of β-cyanoacrylates, catalyzed by ene-reductases (ERs), offers an efficient route to these scaffolds with a high atom economy under mild reaction conditions. However, the narrow substrate acceptance of ER reported in the previous work has limited its application in asymmetric hydrogenation. In this study, we engineered the substrate-binding pocket of an ER from Saccharomyces eubayanus (SeER) to access a panel of chiral β-cyano ester scaffolds with broad structural diversity. Using residue-deletion engineering, mutant M1 was generated and exhibited 416-fold higher catalytic activity toward the model substrate compared to the wt-SeER, along with improved enantioselectivity (from rac to 97% ee). The optimal mutant M4, obtained through saturation mutagenesis and iterative combination, exhibited 1.36 × 104-fold higher catalytic efficiency than that of wt-SeER, and the enantioselectivity further increased to 99.7% ee. Mutant M4 demonstrates broad substrate acceptance and was successfully applied in a gram-scale (200 mM) asymmetric synthesis of Pregabalin (a first-line antiepileptic agent) with 99.7% ee and 65% isolated yield. This study highlights residue deletion as an effective strategy for modifying the ER binding pocket to access the asymmetric hydrogenation of β-cyanoacrylates but also provides valuable engineering guidance for enhancing the substrate acceptance of other ERs possessing similar pockets.
{"title":"Combining Residue Substitution and Deletion Engineering Enhances the Substrate Acceptance of Ene-Reductase for Highly Enantioselective Synthesis of β-Cyano Ester Scaffolds","authors":"An Huang, Yanjun Wan, Xianheng Song, Wenmei Feng, Shuyun Ju, Yajun Wang","doi":"10.1021/acssuschemeng.5c11399","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11399","url":null,"abstract":"Chiral β-cyano ester scaffolds are highly valuable synthons in pharmaceutical synthesis. The direct asymmetric hydrogenation of β-cyanoacrylates, catalyzed by ene-reductases (ERs), offers an efficient route to these scaffolds with a high atom economy under mild reaction conditions. However, the narrow substrate acceptance of ER reported in the previous work has limited its application in asymmetric hydrogenation. In this study, we engineered the substrate-binding pocket of an ER from <i>Saccharomyces eubayanus</i> (<i>Se</i>ER) to access a panel of chiral β-cyano ester scaffolds with broad structural diversity. Using residue-deletion engineering, mutant M1 was generated and exhibited 416-fold higher catalytic activity toward the model substrate compared to the wt-<i>Se</i>ER, along with improved enantioselectivity (from <i>rac</i> to 97% <i>ee</i>). The optimal mutant M4, obtained through saturation mutagenesis and iterative combination, exhibited 1.36 × 10<sup>4</sup>-fold higher catalytic efficiency than that of wt-<i>Se</i>ER, and the enantioselectivity further increased to 99.7% <i>ee</i>. Mutant M4 demonstrates broad substrate acceptance and was successfully applied in a gram-scale (200 mM) asymmetric synthesis of Pregabalin (a first-line antiepileptic agent) with 99.7% <i>ee</i> and 65% isolated yield. This study highlights residue deletion as an effective strategy for modifying the ER binding pocket to access the asymmetric hydrogenation of β-cyanoacrylates but also provides valuable engineering guidance for enhancing the substrate acceptance of other ERs possessing similar pockets.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"79 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089917","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 : 2026-01-29DOI: 10.1021/acssuschemeng.5c12093
Chenshuo Song, Jie Luo, Jun Qiao, Zhongyi Cheng, Qiong Wang, Zhemin Zhou, Laichuang Han
Glutamate decarboxylase (GAD) is a highly specific pyridoxal 5′-phosphate (PLP)-dependent enzyme widely used in the biosynthesis of gamma-aminobutyric acid (GABA), renowned for its high activity, stability, and conversion rate. However, its strict substrate specificity for glutamate confines its application solely to GABA production, and the extremely narrow substrate scope severely limits its potential in synthesizing other valuable amines from diamino acids (e.g., NH2–x–COOH). Here, we report the first successful engineering of selective substrate promiscuity toward structurally similar acidic amino acids in GAD from Escherichia coli (EcGadB). Using a partition-based engineering (PBE) strategy, we simultaneously engineered two key regions: the γ-carboxyl binding site (T62) for substrate affinity and the PLP-binding site (T212) for catalytic efficiency. This yielded double mutants M4D and M4X, which efficiently decarboxylate the non-native substrates l-aspartate and L-2-aminoadipic acid into β-alanine and 5-aminovaleric acid, respectively, while retaining excellent pH adaptability and thermostability. An in vitro crude enzyme system achieved high titers (up to 38 g/L) and near-quantitative conversion (>97%) for 5-aminovaleric acid, outperforming whole-cell catalysis. Molecular dynamics and free energy calculations revealed the mechanistic basis for altered substrate specificity. Our work provides efficient biocatalysts for amine synthesis and a generalizable framework for engineering PLP-dependent enzymes.
{"title":"Partition-Based Engineering of Glutamate Decarboxylase Unlocks Substrate Promiscuity for Synthesis of Nonprotein Amino Acids","authors":"Chenshuo Song, Jie Luo, Jun Qiao, Zhongyi Cheng, Qiong Wang, Zhemin Zhou, Laichuang Han","doi":"10.1021/acssuschemeng.5c12093","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12093","url":null,"abstract":"Glutamate decarboxylase (GAD) is a highly specific pyridoxal 5′-phosphate (PLP)-dependent enzyme widely used in the biosynthesis of gamma-aminobutyric acid (GABA), renowned for its high activity, stability, and conversion rate. However, its strict substrate specificity for glutamate confines its application solely to GABA production, and the extremely narrow substrate scope severely limits its potential in synthesizing other valuable amines from diamino acids (e.g., NH2–<i>x</i>–COOH). Here, we report the first successful engineering of selective substrate promiscuity toward structurally similar acidic amino acids in GAD from <i>Escherichia coli</i> (EcGadB). Using a partition-based engineering (PBE) strategy, we simultaneously engineered two key regions: the γ-carboxyl binding site (T62) for substrate affinity and the PLP-binding site (T212) for catalytic efficiency. This yielded double mutants M4D and M4X, which efficiently decarboxylate the non-native substrates <span>l</span>-aspartate and L-2-aminoadipic acid into β-alanine and 5-aminovaleric acid, respectively, while retaining excellent pH adaptability and thermostability. An in vitro crude enzyme system achieved high titers (up to 38 g/L) and near-quantitative conversion (>97%) for 5-aminovaleric acid, outperforming whole-cell catalysis. Molecular dynamics and free energy calculations revealed the mechanistic basis for altered substrate specificity. Our work provides efficient biocatalysts for amine synthesis and a generalizable framework for engineering PLP-dependent enzymes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070717","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 : 2026-01-29DOI: 10.1021/acssuschemeng.5c12809
Peng Wang, Tao Lu, Qiao-Chu Wang, Min Liu, Xia Feng, Zhijun Gui, Shaobin Li, Wei-Qiang Chen
Copper (Cu) is a bulk trade commodity whose production is carbon-intensive, making embodied carbon transfer (ECT) in its trade an emerging concern. However, a systematic understanding of the evolution and drivers of Cu-related ECT remains limited. This study quantified the historical ECT in global Cu trade using trade flows and country-specific carbon emission intensity (CEI) of Cu and identified the key factors shaping its evolution. Key findings are (1) the ECT in global Cu trade increased by 52% during 2005–2023 and reached 75.3 Mt CO2-eq in 2023, predominantly driven by the trade of Cu concentrate. (2) ECT hotspots have shifted from “North–South” trade to “South–South” trade with 37% of global ECT attributed to the trade between Cu resource-rich economies (e.g., Chile, Peru, Mexico, Kazakhstan) and China. (3) Since 2011, the global ECT has been increasingly driven by trade volume effect, which contributed a 46.2 Mt CO2-eq increase in ECT between 2011 and 2023, although the decline in Cu CEI offset 11% of the cumulative ECT growth during this period. This study offers critical insights for improving the accuracy of ECT and coordinating global decarbonization strategies across global metal supply chains.
{"title":"Unveiling Patterns and Drivers of the Carbon Transfer Embodied in Global Copper Trade","authors":"Peng Wang, Tao Lu, Qiao-Chu Wang, Min Liu, Xia Feng, Zhijun Gui, Shaobin Li, Wei-Qiang Chen","doi":"10.1021/acssuschemeng.5c12809","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12809","url":null,"abstract":"Copper (Cu) is a bulk trade commodity whose production is carbon-intensive, making embodied carbon transfer (ECT) in its trade an emerging concern. However, a systematic understanding of the evolution and drivers of Cu-related ECT remains limited. This study quantified the historical ECT in global Cu trade using trade flows and country-specific carbon emission intensity (CEI) of Cu and identified the key factors shaping its evolution. Key findings are (1) the ECT in global Cu trade increased by 52% during 2005–2023 and reached 75.3 Mt CO<sub>2</sub>-eq in 2023, predominantly driven by the trade of Cu concentrate. (2) ECT hotspots have shifted from “North–South” trade to “South–South” trade with 37% of global ECT attributed to the trade between Cu resource-rich economies (e.g., Chile, Peru, Mexico, Kazakhstan) and China. (3) Since 2011, the global ECT has been increasingly driven by trade volume effect, which contributed a 46.2 Mt CO<sub>2</sub>-eq increase in ECT between 2011 and 2023, although the decline in Cu CEI offset 11% of the cumulative ECT growth during this period. This study offers critical insights for improving the accuracy of ECT and coordinating global decarbonization strategies across global metal supply chains.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098336","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}
Electrooxidation offers a sustainable alternative by utilizing renewable energy to convert biomass-derived cyclohexanol (CHA) to adipic acid (AA), a key industrial chemical for nylon-66 and polyurethane production. While bimetallic Ni-based catalysts enhance the conversion, the role of secondary metals in modulating Ni active-site reconstruction during operation remains unclear, limiting performance optimization. Here, we demonstrate that Cr-doping promoted the dynamic reconstruction of Ni(OH)2 nanosheets to form NiOOH with abundant Ni3+ and oxygen vacancies (OVs), significantly boosting AA electrosynthesis. In situ characterizations reveal that Cr-doping accelerates OH– adsorption and promotes NiOOH formation, while subsequent Cr3+ leaching generates OVs, thus, resolving the long-standing dilemma between stabilizing high-valence Ni and maintaining abundant defects. The optimized catalyst achieves 78.1% AA yield and 85.4% Faradaic efficiency at 1.45 V vs RHE, outperforming undoped Ni(OH)2 and prior systems. Mechanistic studies identify surface Ni3+ and OVs-stabilized *OOH species as the keys for CHA dehydrogenation and cyclohexanone oxidation, respectively. Moreover, a membrane electrode assembly electrolyzer was designed for the efficient coproduction of AA (0.078 mmol h–1 cm–2) and H2 (42.9 mL h–1 cm–2) at a current density of 100 mA cm–2, demonstrating the scalability. This work clarifies the in situ reconstruction of bimetallic sites and provides a design strategy for the efficient electrosynthesis.
电氧化利用可再生能源将生物质衍生的环己醇(CHA)转化为己二酸(AA),这是生产尼龙-66和聚氨酯的关键工业化学品,提供了一种可持续的替代方案。虽然双金属镍基催化剂提高了转化率,但在操作过程中,次生金属在调节Ni活性位点重建中的作用尚不清楚,这限制了性能优化。本研究表明,cr掺杂促进了Ni(OH)2纳米片的动态重构,形成了具有丰富Ni3+和氧空位(OVs)的NiOOH,显著促进了AA的电合成。原位表征表明,cr掺杂加速OH -吸附,促进NiOOH的形成,而随后的Cr3+浸出产生OVs,从而解决了长期以来稳定高价Ni和保持丰富缺陷之间的难题。优化后的催化剂在1.45 V vs RHE下的AA产率为78.1%,法拉第效率为85.4%,优于未掺杂的Ni(OH)2和先前的体系。机理研究发现,表面Ni3+和ovs稳定的*OOH分别是CHA脱氢和环己酮氧化的关键。此外,设计了一个膜电极组合电解槽,在100 mA cm-2的电流密度下,高效地协同生产AA (0.078 mmol h-1 cm-2)和H2 (42.9 mL h-1 cm-2),证明了其可扩展性。这项工作澄清了双金属位点的原位重建,并为有效的电合成提供了设计策略。
{"title":"Cr-Doping Promoted Surface Reconstruction of Ni(OH)2 Electrocatalysts toward Efficient Adipic Acid Electrosynthesis","authors":"Ying Liang, , , Xianping Liao, , , Yingshuai Jia, , , Shiming Guan, , , Wanling Zhang, , , Wenbiao Zhang, , , Yuying Meng, , , Yi Tang*, , and , Qingsheng Gao*, ","doi":"10.1021/acssuschemeng.5c11960","DOIUrl":"10.1021/acssuschemeng.5c11960","url":null,"abstract":"<p >Electrooxidation offers a sustainable alternative by utilizing renewable energy to convert biomass-derived cyclohexanol (CHA) to adipic acid (AA), a key industrial chemical for nylon-66 and polyurethane production. While bimetallic Ni-based catalysts enhance the conversion, the role of secondary metals in modulating Ni active-site reconstruction during operation remains unclear, limiting performance optimization. Here, we demonstrate that Cr-doping promoted the dynamic reconstruction of Ni(OH)<sub>2</sub> nanosheets to form NiOOH with abundant Ni<sup>3+</sup> and oxygen vacancies (OVs), significantly boosting AA electrosynthesis. <i>In situ</i> characterizations reveal that Cr-doping accelerates OH<sup>–</sup> adsorption and promotes NiOOH formation, while subsequent Cr<sup>3+</sup> leaching generates OVs, thus, resolving the long-standing dilemma between stabilizing high-valence Ni and maintaining abundant defects. The optimized catalyst achieves 78.1% AA yield and 85.4% Faradaic efficiency at 1.45 V vs RHE, outperforming undoped Ni(OH)<sub>2</sub> and prior systems. Mechanistic studies identify surface Ni<sup>3+</sup> and OVs-stabilized *OOH species as the keys for CHA dehydrogenation and cyclohexanone oxidation, respectively. Moreover, a membrane electrode assembly electrolyzer was designed for the efficient coproduction of AA (0.078 mmol h<sup>–1</sup> cm<sup>–2</sup>) and H<sub>2</sub> (42.9 mL h<sup>–1</sup> cm<sup>–2</sup>) at a current density of 100 mA cm<sup>–2</sup>, demonstrating the scalability. This work clarifies the <i>in situ</i> reconstruction of bimetallic sites and provides a design strategy for the efficient electrosynthesis.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2583–2594"},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070155","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 : 2026-01-28DOI: 10.1021/acssuschemeng.5c13255
Yue Pan, , , Xin Chen, , , Ming Ye, , , Hao Wu*, , , Xiaolan Xiang, , , Ying Chen, , , Anming Xu, , , Wenming Zhang, , and , Min Jiang,
During succinic acid (SA) biosynthesis, increasing the utilization of CO2 is beneficial for reducing greenhouse gas emissions and lowering production costs. In this study, amine-modified cellulose sponges (AMCS) were prepared, which could decrease more than 80% of CO2 emissions in water by adsorption and chemical reaction. An external fibrous bed bioreactor was filled with AMCS, and the repeated-batch pressurized fermentation was supplied with CO2 micronano bubbles (MNBs) without any carbonates or bicarbonates. In this process, Escherichia coli Suc260-CsgA could form stable biofilms on AMCS, which exhibited significantly enhanced resistance to free radicals. Compared with free-cell batch fermentation under atmospheric pressure, the average productivity of SA and yield were increased by 77.36 and 8.11%. The carbonic anhydrase activity of the biofilm was over 68% higher than that in free-cell fermentation mode, while the actual CO2 utilization increased 2.88-fold. The results indicated that the microbial carbon sequestration was enhanced and the anabolic metabolism of SA was accelerated by the combination of the biofilm, AMCS, and MNBs.
{"title":"Efficient Carbon Dioxide Utilization for Succinic Acid Production by Combination of Amine-Modified Cellulose Sponge, CO2 Micronano Bubbles, and Biofilms","authors":"Yue Pan, , , Xin Chen, , , Ming Ye, , , Hao Wu*, , , Xiaolan Xiang, , , Ying Chen, , , Anming Xu, , , Wenming Zhang, , and , Min Jiang, ","doi":"10.1021/acssuschemeng.5c13255","DOIUrl":"10.1021/acssuschemeng.5c13255","url":null,"abstract":"<p >During succinic acid (SA) biosynthesis, increasing the utilization of CO<sub>2</sub> is beneficial for reducing greenhouse gas emissions and lowering production costs. In this study, amine-modified cellulose sponges (AMCS) were prepared, which could decrease more than 80% of CO<sub>2</sub> emissions in water by adsorption and chemical reaction. An external fibrous bed bioreactor was filled with AMCS, and the repeated-batch pressurized fermentation was supplied with CO<sub>2</sub> micronano bubbles (MNBs) without any carbonates or bicarbonates. In this process, <i>Escherichia coli</i> Suc260-CsgA could form stable biofilms on AMCS, which exhibited significantly enhanced resistance to free radicals. Compared with free-cell batch fermentation under atmospheric pressure, the average productivity of SA and yield were increased by 77.36 and 8.11%. The carbonic anhydrase activity of the biofilm was over 68% higher than that in free-cell fermentation mode, while the actual CO<sub>2</sub> utilization increased 2.88-fold. The results indicated that the microbial carbon sequestration was enhanced and the anabolic metabolism of SA was accelerated by the combination of the biofilm, AMCS, and MNBs.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2701–2711"},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070156","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}
Replacing the sluggish anodic oxygen evolution reaction (OER) with the value-added ethylene glycol oxidation reaction (EGOR) is a promising strategy for energy-efficient hydrogen production. However, achieving high Faradaic efficiency (FE) and selectivity, while elucidating the complex reaction kinetics and mass transport mechanisms coupled with the hydrogen evolution reaction (HER), remains challenging. Herein, a Mo-doped NiCo2O4 electrocatalyst, synthesized via a CTAB-assisted method, achieves >98% FE and >98% selectivity for ethylene glycol (EG) electrooxidation to formic acid (FA) at 100 mA/cm2 in a three-electrode half-cell configuration. Density functional theory (DFT) reveals that Mo doping optimizes the electronic structure, thereby lowering the rate-determining step (RDS) energy barrier for selective FA production. An asymmetric flow field anion exchange membrane (AEM) flow electrolyzer was designed to overcome mass transport limitations, enabling a 143 mV reduction in cell voltage compared to conventional water electrolysis and stable operation over 30 h. In situ electrochemical impedance spectroscopy (EIS) with the distribution of relaxation times (DRT) quantitatively decouples ion transport, charge transfer, and mass transfer resistances under operational conditions. Systematic optimization of current density, flow rate, and EG concentration demonstrated synergistic regulation of kinetics and mass transport. This work provides a high-performance system for the co-production of green hydrogen and valuable chemicals and establishes a universal diagnostic framework for optimizing hybrid electrolysis systems.
{"title":"Elucidating In Situ Impedance Kinetic Mechanisms for Selective Ethylene Glycol Electrooxidation to Formate Production Regulated by Mo-Doped NiCo2O4","authors":"Xinyi Huo, , , Chenhui Wang, , , Fanpeng Ma, , , Guixuan Shan, , , Lin Yang, , , Lingyu Gao, , , Wei Li, , and , Jinli Zhang*, ","doi":"10.1021/acssuschemeng.5c10867","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10867","url":null,"abstract":"<p >Replacing the sluggish anodic oxygen evolution reaction (OER) with the value-added ethylene glycol oxidation reaction (EGOR) is a promising strategy for energy-efficient hydrogen production. However, achieving high Faradaic efficiency (FE) and selectivity, while elucidating the complex reaction kinetics and mass transport mechanisms coupled with the hydrogen evolution reaction (HER), remains challenging. Herein, a Mo-doped NiCo<sub>2</sub>O<sub>4</sub> electrocatalyst, synthesized via a CTAB-assisted method, achieves >98% FE and >98% selectivity for ethylene glycol (EG) electrooxidation to formic acid (FA) at 100 mA/cm<sup>2</sup> in a three-electrode half-cell configuration. Density functional theory (DFT) reveals that Mo doping optimizes the electronic structure, thereby lowering the rate-determining step (RDS) energy barrier for selective FA production. An asymmetric flow field anion exchange membrane (AEM) flow electrolyzer was designed to overcome mass transport limitations, enabling a 143 mV reduction in cell voltage compared to conventional water electrolysis and stable operation over 30 h. <i>In situ</i> electrochemical impedance spectroscopy (EIS) with the distribution of relaxation times (DRT) quantitatively decouples ion transport, charge transfer, and mass transfer resistances under operational conditions. Systematic optimization of current density, flow rate, and EG concentration demonstrated synergistic regulation of kinetics and mass transport. This work provides a high-performance system for the co-production of green hydrogen and valuable chemicals and establishes a universal diagnostic framework for optimizing hybrid electrolysis systems.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2429–2444"},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147048","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}