Pub Date : 2026-03-23DOI: 10.1021/acssuschemeng.5c11786
Ioannis Papaioannou, Maria Ioanna Lilikaki, Athanasios Arampatzis, Ioanna Tzortzi, Xin Gao, Tom Van Gerven, Georgios D. Stefanidis
The transition to nonisocyanate polyurethanes (NIPUs) relies on sustainable routes to precursors like diglycerol dicarbonate (DGC). However, its synthesis via transesterification is hampered by equilibrium limitations, inefficient heat transfer, and high energy demands under conventional heating (CH). This work investigates the transesterification of diglycerol (DIG) with dimethyl carbonate (DMC) under CH and microwave heating (MWH) in batch autoclave reactors. The effects of catalyst loading, DMC:DIG ratio, and temperature were assessed under isothermal and dynamic (temperature-cycling, TC) operation. At 130 °C, MWH achieved 97% DIG conversion and 66% DGC yield, matching the performance of CH at 150 °C. This enhancement is attributed to efficient volumetric heating and methanol removal, which continuously shifts the equilibrium toward product formation. Dynamic MWH via optimized TC further intensified the process, achieving 73% DGC yield with an 85% reduction in reaction time and lower byproduct formation. These findings establish MWH, particularly under optimized dynamic operation, as a versatile intensification platform for equilibrium-limited reactions, enabling faster and more sustainable synthesis of polyurethane precursors.
{"title":"Microwave-Driven Intensification of Diglycerol Transesterification through Dynamic Temperature Operation","authors":"Ioannis Papaioannou, Maria Ioanna Lilikaki, Athanasios Arampatzis, Ioanna Tzortzi, Xin Gao, Tom Van Gerven, Georgios D. Stefanidis","doi":"10.1021/acssuschemeng.5c11786","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11786","url":null,"abstract":"The transition to nonisocyanate polyurethanes (NIPUs) relies on sustainable routes to precursors like diglycerol dicarbonate (DGC). However, its synthesis via transesterification is hampered by equilibrium limitations, inefficient heat transfer, and high energy demands under conventional heating (CH). This work investigates the transesterification of diglycerol (DIG) with dimethyl carbonate (DMC) under CH and microwave heating (MWH) in batch autoclave reactors. The effects of catalyst loading, DMC:DIG ratio, and temperature were assessed under isothermal and dynamic (temperature-cycling, TC) operation. At 130 °C, MWH achieved 97% DIG conversion and 66% DGC yield, matching the performance of CH at 150 °C. This enhancement is attributed to efficient volumetric heating and methanol removal, which continuously shifts the equilibrium toward product formation. Dynamic MWH via optimized TC further intensified the process, achieving 73% DGC yield with an 85% reduction in reaction time and lower byproduct formation. These findings establish MWH, particularly under optimized dynamic operation, as a versatile intensification platform for equilibrium-limited reactions, enabling faster and more sustainable synthesis of polyurethane precursors.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506533","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 : 2026-03-20DOI: 10.1021/acssuschemeng.5c12887
Xiaoqing Lin, Jie Liu, Wenge Cao, Jie Chen, Xiaodong Li, Jianhua Yan
Chemical recycling of wind turbine blades (WTBs) offers a sustainable pathway for waste management, potentially recovering high-quality glass fibers under mild conditions. However, current strategies are hindered by low decomposition efficiencies, slow kinetics, and complex byproduct formation. Herein, we propose a low-temperature cascading decomposition strategy that uniquely integrates acetic acid swelling pretreatment with Ru-Triphos catalysis. Mechanistic investigations revealed that whereas acetic acid swelling effectively disrupts the dense three-dimensional cross-linked epoxy network, the cascading mode mitigates mass transfer resistance by mechanically separating the resin-wrapped fibers. Nonetheless, a critical compatibility issue was identified: residual acetic acid severely inhibits the catalytic cycle by competing for ligand coordination, necessitating an intermediate acid removal step to restore catalyst activity. Under optimal conditions (160 °C, 72 h; swelling–acid removal–cascade), 99% resin decomposition and 95% bisphenol A (BPA) recovery were achieved. The recovered glass fibers exhibited a tensile strength of 1191.1 MPa (97.7% retention of virgin fibers), representing an 829% improvement compared with pyrolyzed fibers. This work establishes a robust protocol for efficient WTB recycling, offering significant potential for integration into industrial-scale dismantling and catalyst closed-loop systems.
{"title":"Dual Roles of Acetic Acid in Wind Turbine Blade Recycling: Mechanistic Insights into Enhanced and Inhibited Decomposition Pathways","authors":"Xiaoqing Lin, Jie Liu, Wenge Cao, Jie Chen, Xiaodong Li, Jianhua Yan","doi":"10.1021/acssuschemeng.5c12887","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12887","url":null,"abstract":"Chemical recycling of wind turbine blades (WTBs) offers a sustainable pathway for waste management, potentially recovering high-quality glass fibers under mild conditions. However, current strategies are hindered by low decomposition efficiencies, slow kinetics, and complex byproduct formation. Herein, we propose a low-temperature cascading decomposition strategy that uniquely integrates acetic acid swelling pretreatment with Ru-Triphos catalysis. Mechanistic investigations revealed that whereas acetic acid swelling effectively disrupts the dense three-dimensional cross-linked epoxy network, the cascading mode mitigates mass transfer resistance by mechanically separating the resin-wrapped fibers. Nonetheless, a critical compatibility issue was identified: residual acetic acid severely inhibits the catalytic cycle by competing for ligand coordination, necessitating an intermediate acid removal step to restore catalyst activity. Under optimal conditions (160 °C, 72 h; swelling–acid removal–cascade), 99% resin decomposition and 95% bisphenol A (BPA) recovery were achieved. The recovered glass fibers exhibited a tensile strength of 1191.1 MPa (97.7% retention of virgin fibers), representing an 829% improvement compared with pyrolyzed fibers. This work establishes a robust protocol for efficient WTB recycling, offering significant potential for integration into industrial-scale dismantling and catalyst closed-loop systems.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"85 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489526","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}
Methanol steam reforming is a popular technology for hydrogen production, but it usually suffers from the methanation side reaction and low hydrogen yield. Herein, a novel K-doped Ru/CeO2 catalyst was proposed to suppress methanation and enhance hydrogen production. The Ru-5K/CeO2 catalyst doped with 5 wt % K achieves 100% methanol conversion, a 0.578 mol·g–1·h–1 hydrogen production rate, and 66.4% hydrogen selectivity at 450 °C, with only 3.6% CH4, which is much better than other Ru–K/CeO2 catalysts. Under the same conditions, Ru/CeO2 and Ru-10K/CeO2 only achieve 0.268 mol·g–1·h–1 and 0.224 mol·g–1·h–1 hydrogen production rates, 64.1% and 64.5% hydrogen selectivity, respectively. The promotion effect and mechanism of K doping on the methanation suppression of Ru/CeO2 catalysts in the methanol steam reforming process were investigated in detail. Characterization and experimental results show that suitable K doping in the Ru/CeO2 catalyst enhances the metal–carrier interactions and induces the formation of abundant oxygen vacancies at the same time. And the hydrogen atom dissociation and water–gas shift reactions on the catalyst surface are promoted significantly. Additionally, in situ DRIFTS characterization presents that the Ru-5K/CeO2 catalyst dominates the formation of the bridged carbonyl (Ru-CO-K) intermediate. This inhibits methane formation due to the interaction between Ru and K, and strengthens the connection of CO generated by methanol decomposition. The increase in K leads to the formation of abundant oxygen vacancies in CeO2, which promotes the dissociation of water to form hydroxyl groups and hydrogen and facilitates the water–gas shift reaction. The conversion of bridged carbonyl groups to CO2 and H2 is also accelerated, and methane formation through this dual regulatory mechanism is thus inhibited. This work offers fresh perspectives and a useful reference for hydrogen production, contributing to the ongoing discussion on the role of alkali metals in promoting methanol steam reforming.
{"title":"Methanation Suppression and Hydrogen Production Enhancement in Methanol Steam Reforming by K-Doped Ru/CeO2 Catalyst","authors":"Riyang Shu, Haozhe Huang, Bin Hu, Long Xie, Xintong Chen, Zhipeng Tian, Chao Wang, Jingtao Zhang, Sheng Yang, Xianglong Luo, Ying Chen","doi":"10.1021/acssuschemeng.5c14228","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14228","url":null,"abstract":"Methanol steam reforming is a popular technology for hydrogen production, but it usually suffers from the methanation side reaction and low hydrogen yield. Herein, a novel K-doped Ru/CeO<sub>2</sub> catalyst was proposed to suppress methanation and enhance hydrogen production. The Ru-5K/CeO<sub>2</sub> catalyst doped with 5 wt % K achieves 100% methanol conversion, a 0.578 mol·g<sup>–1</sup>·h<sup>–1</sup> hydrogen production rate, and 66.4% hydrogen selectivity at 450 °C, with only 3.6% CH<sub>4</sub>, which is much better than other Ru–K/CeO<sub>2</sub> catalysts. Under the same conditions, Ru/CeO<sub>2</sub> and Ru-10K/CeO<sub>2</sub> only achieve 0.268 mol·g<sup>–1</sup>·h<sup>–1</sup> and 0.224 mol·g<sup>–1</sup>·h<sup>–1</sup> hydrogen production rates, 64.1% and 64.5% hydrogen selectivity, respectively. The promotion effect and mechanism of K doping on the methanation suppression of Ru/CeO<sub>2</sub> catalysts in the methanol steam reforming process were investigated in detail. Characterization and experimental results show that suitable K doping in the Ru/CeO<sub>2</sub> catalyst enhances the metal–carrier interactions and induces the formation of abundant oxygen vacancies at the same time. And the hydrogen atom dissociation and water–gas shift reactions on the catalyst surface are promoted significantly. Additionally, <i>in situ</i> DRIFTS characterization presents that the Ru-5K/CeO<sub>2</sub> catalyst dominates the formation of the bridged carbonyl (Ru-CO-K) intermediate. This inhibits methane formation due to the interaction between Ru and K, and strengthens the connection of CO generated by methanol decomposition. The increase in K leads to the formation of abundant oxygen vacancies in CeO<sub>2</sub>, which promotes the dissociation of water to form hydroxyl groups and hydrogen and facilitates the water–gas shift reaction. The conversion of bridged carbonyl groups to CO<sub>2</sub> and H<sub>2</sub> is also accelerated, and methane formation through this dual regulatory mechanism is thus inhibited. This work offers fresh perspectives and a useful reference for hydrogen production, contributing to the ongoing discussion on the role of alkali metals in promoting methanol steam reforming.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489527","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}
In recent years, the cocombustion of zero-carbon fuel NH3 with biomass-derived sewage sludge (SS) represents a promising pathway to reduce CO2 emissions. Ash produced during sewage sludge combustion has been identified as a major factor influencing the NH3 oxidation pathway. As pure reagents fail to reproduce the realistic effects of complex mineral interfaces in sewage sludge ash, a fixed-bed reactor system coupled to an Fourier-transform infrared (FTIR) gas analyzer was therefore established in this study. In combination with NH3-TPD, H2-TPR, electron paramagnetic resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS), and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterizations, the oxidation behavior of NH3 in the presence of authentic sewage sludge ash under different conditions was systematically investigated, with particular emphasis on elucidating the decisive roles of CaO and Fe2O3. The presence of SSA increased the NH3 conversion and shifted the oxidation pathways. CaO provided abundant Lewis acid sites that strongly adsorbed and activated NH3 to form NHX species, which preferentially reacted with O2, thereby governing the NO pathway under most conditions. At higher NH3 concentrations, Fe2O3 sustained Fe3+/Fe2+ redox and lattice-oxygen migration, promoting coupling between NHX and NO to N2. These results establish a foundation for the large-scale, efficient, and clean deployment of NH3 as a zero-carbon fuel.
{"title":"NH3 Oxidation Pathways in the Presence of Sewage Sludge Ash: Focusing on the Mechanistic Roles of CaO and Fe2O3","authors":"Wenhe Liu, Jiangtao Meng, Yanhong Hao, Yuanyuan Zhang, Jing Wang†, Fei Wang, Fangqin Cheng","doi":"10.1021/acssuschemeng.6c00432","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00432","url":null,"abstract":"In recent years, the cocombustion of zero-carbon fuel NH<sub>3</sub> with biomass-derived sewage sludge (SS) represents a promising pathway to reduce CO<sub>2</sub> emissions. Ash produced during sewage sludge combustion has been identified as a major factor influencing the NH<sub>3</sub> oxidation pathway. As pure reagents fail to reproduce the realistic effects of complex mineral interfaces in sewage sludge ash, a fixed-bed reactor system coupled to an Fourier-transform infrared (FTIR) gas analyzer was therefore established in this study. In combination with NH<sub>3</sub>-TPD, H<sub>2</sub>-TPR, electron paramagnetic resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS), and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterizations, the oxidation behavior of NH<sub>3</sub> in the presence of authentic sewage sludge ash under different conditions was systematically investigated, with particular emphasis on elucidating the decisive roles of CaO and Fe<sub>2</sub>O<sub>3</sub>. The presence of SSA increased the NH<sub>3</sub> conversion and shifted the oxidation pathways. CaO provided abundant Lewis acid sites that strongly adsorbed and activated NH<sub>3</sub> to form NH<sub>X</sub> species, which preferentially reacted with O<sub>2</sub>, thereby governing the NO pathway under most conditions. At higher NH<sub>3</sub> concentrations, Fe<sub>2</sub>O<sub>3</sub> sustained Fe<sup>3+</sup>/Fe<sup>2+</sup> redox and lattice-oxygen migration, promoting coupling between NH<sub>X</sub> and NO to N<sub>2</sub>. These results establish a foundation for the large-scale, efficient, and clean deployment of NH<sub>3</sub> as a zero-carbon fuel.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489528","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 : 2026-03-19DOI: 10.1021/acssuschemeng.6c02612
Boran Yang, Xingcheng Ma, Hongli Wang, Ruiqi Yao, Aiyang Li, Zixin A, Zaihang Zheng, Ying Han, Xu Ran
On page 4152, the following sentences should be deleted: “The band structures of Fe2O3, NiFe2O4, and Fe2O3/NiFe2O4 were further investigated by ultraviolet–visible diffuse reflectance spectroscopy and ultraviolet photoelectron spectroscopy (UPS). FeP/Fe3O4@C held a narrower energy gap (Eg = 0.98 eV) than Fe3O4@C (Eg = 1.64 eV) (Figure 2h), attributable to heterointerface-induced midgap/impurity levels into the band structure. indicating the presence of reinforced electronic interactions between Fe2O3 and NiFe2O4.” Later in the same paragraph on page 4152, the following sentences should be replaced: “UPS results show that Fe2O3 has a lower work function (3.12 eV) than NiFe2O4 (3.64 eV), providing a driving force for interfacial electron transfer (Figure S3). Upon heterostructure formation, electron redistribution leads to a modified work function (3.42 eV) and the generation of an internal electric field.” The corrected sentences are as follows: “UPS results show that Fe2O3 has a lower work function (3.10 eV) than NiFe2O4 (3.64 eV), providing a driving force for interfacial electron transfer (Figure S3). Upon heterostructure formation, electron redistribution leads to a modified work function (3.47 eV) and the generation of an internal electric field.” This article has not yet been cited by other publications.
{"title":"Correction to “Highly Efficient Electrochemical Nitrate Reduction to Ammonia over a Fe2O3/NiFe2O4 Heterostructured Catalyst”","authors":"Boran Yang, Xingcheng Ma, Hongli Wang, Ruiqi Yao, Aiyang Li, Zixin A, Zaihang Zheng, Ying Han, Xu Ran","doi":"10.1021/acssuschemeng.6c02612","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c02612","url":null,"abstract":"On page 4152, the following sentences should be deleted: “The band structures of Fe<sub>2</sub>O<sub>3</sub>, NiFe<sub>2</sub>O<sub>4</sub>, and Fe<sub>2</sub>O<sub>3</sub>/NiFe<sub>2</sub>O<sub>4</sub> were further investigated by ultraviolet–visible diffuse reflectance spectroscopy and ultraviolet photoelectron spectroscopy (UPS). FeP/Fe<sub>3</sub>O<sub>4</sub>@C held a narrower energy gap (Eg = 0.98 eV) than Fe<sub>3</sub>O<sub>4</sub>@C (Eg = 1.64 eV) (Figure 2h), attributable to heterointerface-induced midgap/impurity levels into the band structure. indicating the presence of reinforced electronic interactions between Fe<sub>2</sub>O<sub>3</sub> and NiFe<sub>2</sub>O<sub>4</sub>.” Later in the same paragraph on page 4152, the following sentences should be replaced: “UPS results show that Fe<sub>2</sub>O<sub>3</sub> has a lower work function (3.12 eV) than NiFe<sub>2</sub>O<sub>4</sub> (3.64 eV), providing a driving force for interfacial electron transfer (Figure S3). Upon heterostructure formation, electron redistribution leads to a modified work function (3.42 eV) and the generation of an internal electric field.” The corrected sentences are as follows: “UPS results show that Fe<sub>2</sub>O<sub>3</sub> has a lower work function (3.10 eV) than NiFe<sub>2</sub>O<sub>4</sub> (3.64 eV), providing a driving force for interfacial electron transfer (Figure S3). Upon heterostructure formation, electron redistribution leads to a modified work function (3.47 eV) and the generation of an internal electric field.” This article has not yet been cited by other publications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489530","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 : 2026-03-19DOI: 10.1021/acssuschemeng.5c11885
Aymane El Bouhali, Frédéric Addiego, Hande Barkan-Öztürk, Alexander Bismarck, Jean-Sébastien Thomann, Daniel F. Schmidt
Lignin, a renewable biopolymer, presents significant potential for sustainable materials development, particularly in the synthesis of porous adsorbents for water treatment. This study introduces a tailored approach for synthesizing lignin-based xerogels (LBX) via a sol–gel process combined with polymerization-induced phase separation (PIPS), enabling a controlled pore morphology and hierarchy. Data on lignin structure and molecular weight are used to effectively predict the outcome of the sol–gel process prior to the incorporation of polyethylene glycol (PEG) as an additive polymer. By systematically varying the molecular weight and concentration of PEG, the influence of these factors on phase separation dynamics, drying behavior, and the structure of the resulting porous bodies is revealed. The synthesized xerogels exhibited tunable pore structures, with average pore sizes ranging from 10 to 90 μm, porosities between 19 and 73 vol %, specific surface areas (SSAs) from 0.7 to 13.2 m2/g, and permeability values spanning 1.3 to 5.6 darcys. This study highlights a tunable strategy for lignin valorization, offering insights into the development of biobased porous materials with potential relevance to heavy metal adsorption.
{"title":"Tailored Lignin Xerogels: Insights into Morphology Control","authors":"Aymane El Bouhali, Frédéric Addiego, Hande Barkan-Öztürk, Alexander Bismarck, Jean-Sébastien Thomann, Daniel F. Schmidt","doi":"10.1021/acssuschemeng.5c11885","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11885","url":null,"abstract":"Lignin, a renewable biopolymer, presents significant potential for sustainable materials development, particularly in the synthesis of porous adsorbents for water treatment. This study introduces a tailored approach for synthesizing lignin-based xerogels (LBX) via a sol–gel process combined with polymerization-induced phase separation (PIPS), enabling a controlled pore morphology and hierarchy. Data on lignin structure and molecular weight are used to effectively predict the outcome of the sol–gel process prior to the incorporation of polyethylene glycol (PEG) as an additive polymer. By systematically varying the molecular weight and concentration of PEG, the influence of these factors on phase separation dynamics, drying behavior, and the structure of the resulting porous bodies is revealed. The synthesized xerogels exhibited tunable pore structures, with average pore sizes ranging from 10 to 90 μm, porosities between 19 and 73 vol %, specific surface areas (SSAs) from 0.7 to 13.2 m<sup>2</sup>/g, and permeability values spanning 1.3 to 5.6 darcys. This study highlights a tunable strategy for lignin valorization, offering insights into the development of biobased porous materials with potential relevance to heavy metal adsorption.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"49 3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489529","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 : 2026-03-19DOI: 10.1021/acssuschemeng.5c08725
Arslan Khurram, Sadaf Mutahir, Muhammad Asim Khan, Abdul Jabbar, Wenhao Liu, Akhtar Munir, Sameerah I. Al-Saeedi
The development of efficient photocatalysts for selective organic transformations under mild conditions remains a pivotal challenge in sustainable chemistry. This study presents a novel S-scheme heterojunction photocatalyst composed of nickel–iron layered double hydroxide (NiFe-LDH) and boron-doped graphitic carbon nitride (BCN) for the selective oxidation of benzyl alcohol (BA) to benzaldehyde (BAD). Systematic optimization revealed that the 20% NiFe-LDH@BCN composite achieves 88% BA conversion with 99% BAD selectivity under visible light, outperforming pristine NiFe-LDH and BCN by 1.8- and 2-fold, respectively. Advanced characterization techniques (XRD, XPS, TEM, HRTEM, EDS, EPR) and density functional theory (DFT) calculations elucidated the synergistic mechanisms: boron doping tailors the electronic structure of BCN, introducing Lewis acid sites for enhanced substrate adsorption, while the S-scheme charge transfer between NiFe-LDH and BCN suppresses recombination and preserves strong redox potentials (+2.24 eV for oxidation, −0.57 eV for reduction). The heterostructure exhibits extended visible-light absorption (550 nm) and a reduced bandgap (1.94 eV vs 2.66 eV for BCN), attributed to interfacial electronic coupling. In situ DRIFTS and radical trapping experiments identified hole-mediated α-H abstraction and superoxide-assisted dehydrogenation as the dominant pathway, ensuring high selectivity without toxic byproducts. The catalyst retains 88% conversion and >99% selectivity over four cycles, demonstrating exceptional stability. This work not only advances the fundamental understanding of S-scheme heterojunctions but also establishes a sustainable photocatalytic paradigm, replacing hazardous oxidants with solar-driven atmospheric oxygen, offering a scalable and eco-friendly route for selective organic synthesis.
在温和条件下，开发用于选择性有机转化的高效光催化剂仍然是可持续化学的关键挑战。研究了一种由镍铁层状双氢氧化物（NiFe-LDH）和掺硼石墨氮化碳（BCN）组成的新型s型异质结光催化剂，用于苯甲醇（BA）的选择性氧化制备苯甲醛（BAD）。系统优化表明，20% NiFe-LDH@BCN复合材料在可见光下的BA转化率为88%，BAD选择性为99%，分别比原始NiFe-LDH和BCN高1.8倍和2倍。先进的表征技术（XRD， XPS， TEM， HRTEM， EDS， EPR）和密度泛函数理论（DFT）计算阐明了协同机制：硼掺杂调整了BCN的电子结构，引入Lewis酸位点以增强底物吸附，而nfe - ldh和BCN之间的S-scheme电荷转移抑制了重组并保持了强氧化还原电位（氧化+2.24 eV，还原- 0.57 eV）。由于界面电子耦合，该异质结构具有更大的可见光吸收（550 nm）和更小的带隙（1.94 eV vs 2.66 eV）。原位漂移和自由基捕获实验发现，空穴介导的α-H提取和超氧化物辅助脱氢是主要途径，确保了高选择性和无毒副产物。该催化剂在四个循环中保持88%的转化率和99%的选择性，表现出优异的稳定性。这项工作不仅推进了对s型异质结的基本理解，而且建立了可持续的光催化范例，用太阳能驱动的大气氧气取代有害的氧化剂，为选择性有机合成提供了可扩展和环保的途径。
{"title":"Interfacial Engineering of NiFe-LDH@BCN S-Scheme Heterojunctions for Selective Photocatalytic Alcohol Oxidation: From Band Alignment to Molecular Activation","authors":"Arslan Khurram, Sadaf Mutahir, Muhammad Asim Khan, Abdul Jabbar, Wenhao Liu, Akhtar Munir, Sameerah I. Al-Saeedi","doi":"10.1021/acssuschemeng.5c08725","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c08725","url":null,"abstract":"The development of efficient photocatalysts for selective organic transformations under mild conditions remains a pivotal challenge in sustainable chemistry. This study presents a novel S-scheme heterojunction photocatalyst composed of nickel–iron layered double hydroxide (NiFe-LDH) and boron-doped graphitic carbon nitride (BCN) for the selective oxidation of benzyl alcohol (BA) to benzaldehyde (BAD). Systematic optimization revealed that the 20% NiFe-LDH@BCN composite achieves 88% BA conversion with 99% BAD selectivity under visible light, outperforming pristine NiFe-LDH and BCN by 1.8- and 2-fold, respectively. Advanced characterization techniques (XRD, XPS, TEM, HRTEM, EDS, EPR) and density functional theory (DFT) calculations elucidated the synergistic mechanisms: boron doping tailors the electronic structure of BCN, introducing Lewis acid sites for enhanced substrate adsorption, while the S-scheme charge transfer between NiFe-LDH and BCN suppresses recombination and preserves strong redox potentials (+2.24 eV for oxidation, −0.57 eV for reduction). The heterostructure exhibits extended visible-light absorption (550 nm) and a reduced bandgap (1.94 eV vs 2.66 eV for BCN), attributed to interfacial electronic coupling. In situ DRIFTS and radical trapping experiments identified hole-mediated α-H abstraction and superoxide-assisted dehydrogenation as the dominant pathway, ensuring high selectivity without toxic byproducts. The catalyst retains 88% conversion and >99% selectivity over four cycles, demonstrating exceptional stability. This work not only advances the fundamental understanding of S-scheme heterojunctions but also establishes a sustainable photocatalytic paradigm, replacing hazardous oxidants with solar-driven atmospheric oxygen, offering a scalable and eco-friendly route for selective organic synthesis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478109","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 electrocatalytic carbon dioxide reduction reaction (ECO2RR) has emerged as a key strategy for mitigating the greenhouse effect and addressing energy shortages due to their mild reaction conditions and high controllability. Carbon-based catalysts, characterized by their low cost, high specific surface area, high conductivity, and excellent chemical stability, are emerging as alternatives to precious-metal systems. Their catalytic performance ─ activity, stability, and selectivity ─ can be modulated through coordination, size, and synergistic effects, driving the strategic design of doped carbon materials (e.g., via heteroatom or metal doping) to optimize active sites, tailor electronic structures, and steer reaction pathways. However, the practical implementation depends not only on catalytic performance but equally on overarching systemic factors of sustainability and economic viability. Life Cycle Assessment (LCA) and Technology-Economic Analysis (TEA) underscore that the environmental footprint and commercial feasibility of ECO2RR systems are fundamentally governed by the integration of renewable electricity and optimized process design, respectively. Also, this paper systematically reviews the reaction pathways and product distributions of carbon-based catalysts in ECO2RR. Subsequently, it analyzes the influence of key factors such as potential, pH, electrolyte type, reactor design, and CO2 source on reaction performance, aiming to improve the interaction between reactants and reaction efficiency. Additionally, the applications of single-atom and multiatom doped carbon-based catalysts for the ECO2RR were discussed, with an emphasis on their underlying reaction mechanisms. Finally, this article concludes by highlighting the major challenges and prospects associated with carbon-based catalysts in ECO2RR, providing valuable insights for future research and development.
{"title":"Carbon-Based Catalysts for Electrocatalytic CO2 Reduction Reaction via Heteroatom Doping and Metal Doping: Influencing Factors, Mechanisms, and Economic Analysis","authors":"Tiantian Yang, Zhixiang Tang, Junchi Liu, Wenwen Kong, Lianfei Xu, Zhijiang Dong, Honghong Lyu, Boxiong Shen","doi":"10.1021/acssuschemeng.5c09060","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09060","url":null,"abstract":"The electrocatalytic carbon dioxide reduction reaction (ECO<sub>2</sub>RR) has emerged as a key strategy for mitigating the greenhouse effect and addressing energy shortages due to their mild reaction conditions and high controllability. Carbon-based catalysts, characterized by their low cost, high specific surface area, high conductivity, and excellent chemical stability, are emerging as alternatives to precious-metal systems. Their catalytic performance ─ activity, stability, and selectivity ─ can be modulated through coordination, size, and synergistic effects, driving the strategic design of doped carbon materials (e.g., via heteroatom or metal doping) to optimize active sites, tailor electronic structures, and steer reaction pathways. However, the practical implementation depends not only on catalytic performance but equally on overarching systemic factors of sustainability and economic viability. Life Cycle Assessment (LCA) and Technology-Economic Analysis (TEA) underscore that the environmental footprint and commercial feasibility of ECO<sub>2</sub>RR systems are fundamentally governed by the integration of renewable electricity and optimized process design, respectively. Also, this paper systematically reviews the reaction pathways and product distributions of carbon-based catalysts in ECO<sub>2</sub>RR. Subsequently, it analyzes the influence of key factors such as potential, pH, electrolyte type, reactor design, and CO<sub>2</sub> source on reaction performance, aiming to improve the interaction between reactants and reaction efficiency. Additionally, the applications of single-atom and multiatom doped carbon-based catalysts for the ECO<sub>2</sub>RR were discussed, with an emphasis on their underlying reaction mechanisms. Finally, this article concludes by highlighting the major challenges and prospects associated with carbon-based catalysts in ECO<sub>2</sub>RR, providing valuable insights for future research and development.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471093","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 : 2026-03-18DOI: 10.1021/acssuschemeng.5c12096
Aishwarya D. A, Srisowmeya Guruchandran, Swathi Sudhakar, Ethayaraja Mani
3D printing of materials allows rapid and cost-effective fabrication of complex geometries and customized features in product design. With increasing focus on sustainability and circularity, natural biopolymers have gained attention as eco-friendly alternatives for developing 3D printing inks. Among these, zein, a prolamin-rich protein derived as a byproduct from corn processing, is desirable due to its biodegradability, biocompatibility, and availability in large scale. However, native zein ink prepared in aqueous ethanolic solution suffers from poor printability, structural infidelity, nozzle clogging, and solvent evaporation, which significantly compromise its usability. In this study, deep eutectic solvents (DES) are used to prepare zein inks for 3D printing applications. Rheological studies confirmed shear-thinning behavior of the formulated eutectic zein inks with tan δ < 1, indicating a favorable viscoelastic profile for 3D printing. Optimized printing conditions for the formulated ink are found to be 20 mm/s speed, 90 kPa pressure, 45% infill, and 22G (0.41 mm) nozzle diameter. Further, the formulated inks exhibited improved performance, such as increased filament stability, reduced collapse, and enhanced structural integrity over the native zein inks. In addition to ink compliance for 3D printing, cell adhesion studies revealed excellent biocompatibility and fibroblast proliferation, underscoring the material’s potential for biomedical applications. The findings of the study present a promising material formulation for sustainable and eco-friendly 3D printable bioinks in biomedical applications.
{"title":"Deep Eutectic Solvent-Based 3D Printable Zein Ink","authors":"Aishwarya D. A, Srisowmeya Guruchandran, Swathi Sudhakar, Ethayaraja Mani","doi":"10.1021/acssuschemeng.5c12096","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12096","url":null,"abstract":"3D printing of materials allows rapid and cost-effective fabrication of complex geometries and customized features in product design. With increasing focus on sustainability and circularity, natural biopolymers have gained attention as eco-friendly alternatives for developing 3D printing inks. Among these, zein, a prolamin-rich protein derived as a byproduct from corn processing, is desirable due to its biodegradability, biocompatibility, and availability in large scale. However, native zein ink prepared in aqueous ethanolic solution suffers from poor printability, structural infidelity, nozzle clogging, and solvent evaporation, which significantly compromise its usability. In this study, deep eutectic solvents (DES) are used to prepare zein inks for 3D printing applications. Rheological studies confirmed shear-thinning behavior of the formulated eutectic zein inks with tan δ < 1, indicating a favorable viscoelastic profile for 3D printing. Optimized printing conditions for the formulated ink are found to be 20 mm/s speed, 90 kPa pressure, 45% infill, and 22G (0.41 mm) nozzle diameter. Further, the formulated inks exhibited improved performance, such as increased filament stability, reduced collapse, and enhanced structural integrity over the native zein inks. In addition to ink compliance for 3D printing, cell adhesion studies revealed excellent biocompatibility and fibroblast proliferation, underscoring the material’s potential for biomedical applications. The findings of the study present a promising material formulation for sustainable and eco-friendly 3D printable bioinks in biomedical applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"273 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478057","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 : 2026-03-18DOI: 10.1021/acssuschemeng.5c14176
Wenqin Zhao, Xinming Kong, Xiwen Huang, Zonghao Zhang, Lei Huang, Pingle Liu
The rational design of catalyst structures is pivotal for achieving high activity and selectivity in hydrodeoxygenation (HDO) reactions. However, simultaneously promoting aromatic ring hydrogenation while selectively cleaving C–O(R) bonds remains a significant challenge. In this work, a series of boron-doped carbon nanotube-supported Ni–Co alloy nanoparticles (Ni–Co/BCNTs) catalysts were developed for the selective HDO of guaiacol to cyclohexanol. Comprehensive characterizations reveal that Co incorporation induces electron-rich Ni and facilitates the formation of smaller Ni–Co alloy nanoparticles, thus enhancing catalytic activity. Boron doping further promotes the dispersion of active metal nanoparticles and increases surface acidity, thereby accelerating the demethoxylation of the intermediate 2-methoxycyclohexanol to cyclohexanol. Density functional theory (DFT) calculations confirm that the superior performance of the bimetallic system originates from the enhanced adsorption of both H2 and guaiacol, as well as reduced energy barriers for the HDO of guaiacol. Finally, 15Ni–7.5Co/BCNTs achieve a cyclohexanol yield of 93.8% and exhibit excellent stability. This study offers a novel and effective strategy for designing efficient bimetallic catalysts for biomass-derived phenolic HDO.
{"title":"Boron-Doped Carbon Nanotubes Supported Ni–Co Bimetallic Catalyst for Selective Hydrodeoxygenation of Guaiacol to Cyclohexanol","authors":"Wenqin Zhao, Xinming Kong, Xiwen Huang, Zonghao Zhang, Lei Huang, Pingle Liu","doi":"10.1021/acssuschemeng.5c14176","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14176","url":null,"abstract":"The rational design of catalyst structures is pivotal for achieving high activity and selectivity in hydrodeoxygenation (HDO) reactions. However, simultaneously promoting aromatic ring hydrogenation while selectively cleaving C–O(R) bonds remains a significant challenge. In this work, a series of boron-doped carbon nanotube-supported Ni–Co alloy nanoparticles (Ni–Co/BCNTs) catalysts were developed for the selective HDO of guaiacol to cyclohexanol. Comprehensive characterizations reveal that Co incorporation induces electron-rich Ni and facilitates the formation of smaller Ni–Co alloy nanoparticles, thus enhancing catalytic activity. Boron doping further promotes the dispersion of active metal nanoparticles and increases surface acidity, thereby accelerating the demethoxylation of the intermediate 2-methoxycyclohexanol to cyclohexanol. Density functional theory (DFT) calculations confirm that the superior performance of the bimetallic system originates from the enhanced adsorption of both H<sub>2</sub> and guaiacol, as well as reduced energy barriers for the HDO of guaiacol. Finally, 15Ni–7.5Co/BCNTs achieve a cyclohexanol yield of 93.8% and exhibit excellent stability. This study offers a novel and effective strategy for designing efficient bimetallic catalysts for biomass-derived phenolic HDO.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471094","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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