Pub Date : 2024-10-22DOI: 10.1021/acssuschemeng.4c04684
Ye Liu, Haiyang Yuan, Bin Zhang, Lei Zhang, Qingling Xu, Minghua Dong, Tianjiao Wang, Xiaomeng Cheng, Haifeng Qi, Zhijuan Zhao, Lihua Chen, Baolian Su, Buxing Han, Huizhen Liu
Selective hydrogenation of substrates containing multiple unsaturated bonds (C═C and C═O) is a crucial catalytic process in the production of high-value chemicals. The development of nonprecious metal catalytic systems is of importance for hydrogenation processes due to the high cost and scarcity of noble metals. In this study, we have developed a straightforward and versatile encapsulation technique for the synthesis of Ni@NbOx catalysts, which enables highly selective hydrodehydroxylation of 5-hydroxymethylfurfural (HMF) to 5-methylfurfural (MF) under H2. Mechanistic studies revealed that metallic Ni0 encapsulated within NbOx facilitates hydrogen dissociation through an energy quasi-barrierless process (<0.1 eV), while simultaneously avoiding the adsorption of furan or C═O groups over Ni nanoparticles, therefore enhancing the selective hydrodehydroxylation of HMF to MF. Furthermore, the Ni@NbOx catalyst was tolerant to different conditions for selective hydrogenation, such as crude H2 containing CO, substrates contaminated with various metal salts, etc.
{"title":"Non-noble Ni@NbOx Catalyst for Selective Hydrodehydroxylation of 5-Hydroxymethylfurfural to 5-Methylfurfural","authors":"Ye Liu, Haiyang Yuan, Bin Zhang, Lei Zhang, Qingling Xu, Minghua Dong, Tianjiao Wang, Xiaomeng Cheng, Haifeng Qi, Zhijuan Zhao, Lihua Chen, Baolian Su, Buxing Han, Huizhen Liu","doi":"10.1021/acssuschemeng.4c04684","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04684","url":null,"abstract":"Selective hydrogenation of substrates containing multiple unsaturated bonds (C═C and C═O) is a crucial catalytic process in the production of high-value chemicals. The development of nonprecious metal catalytic systems is of importance for hydrogenation processes due to the high cost and scarcity of noble metals. In this study, we have developed a straightforward and versatile encapsulation technique for the synthesis of Ni@NbO<sub><i>x</i></sub> catalysts, which enables highly selective hydrodehydroxylation of 5-hydroxymethylfurfural (HMF) to 5-methylfurfural (MF) under H<sub>2</sub>. Mechanistic studies revealed that metallic Ni<sup>0</sup> encapsulated within NbO<sub><i>x</i></sub> facilitates hydrogen dissociation through an energy quasi-barrierless process (<0.1 eV), while simultaneously avoiding the adsorption of furan or C═O groups over Ni nanoparticles, therefore enhancing the selective hydrodehydroxylation of HMF to MF. Furthermore, the Ni@NbO<sub><i>x</i></sub> catalyst was tolerant to different conditions for selective hydrogenation, such as crude H<sub>2</sub> containing CO, substrates contaminated with various metal salts, etc.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486431","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 this contribution, several hierarchical zeolites comprising mainly Brønsted acid sites with different morphologies (nanosheets, nanoparticles, nanorods) were synthesized and applied to the efficient synthesis of the perfume Florol (2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol) via Prins cyclization of isoprenol and isovaraldehyde. Tuning the acidity in a zeolite was done by either incorporating metal centers or changing the initial composition and crystallization time. Furthermore, the interplay among the pore structure, specific mesoporosity, and accessibility of acidic sites is crucial for optimizing Florol synthesis. Strong Brønsted acid sites enhance the formation of the dehydration products, while mild-acidic Brønsted acid sites with a medium strength of accessible acid sites improve the formation of Florol. A maximum Florol yield of ca. 80% was achieved with Al-MFI and Al-FER (only 30 min) with typical nanosheet (nsh) morphology; in addition, values of TOF in the order of 1121 and 2655 h–1, respectively, were also achieved. Al-FER-nsh showed itself to be robust, because it can be reused several times without any apparent loss of its catalytic activity. Finally, different green chemistry parameters were also applied to the studied zeolites in the synthesis of Florol, suggesting the high efficiency of the best catalyst (Al-MFI-nsh).
{"title":"Fine-Tuning of Acidity in Hierarchical Zeolites for the Efficient Prins Cyclization Yielding Florol","authors":"Julián E. Sánchez-Velandia, Mykhailo Kurmach, Oleksiy Shvets, Hermenegildo Garcia Baldoví, Eduardo García-Verdugo, Dmitry Yu. Murzin, Nataliya Shcherban","doi":"10.1021/acssuschemeng.4c05535","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05535","url":null,"abstract":"In this contribution, several hierarchical zeolites comprising mainly Brønsted acid sites with different morphologies (nanosheets, nanoparticles, nanorods) were synthesized and applied to the efficient synthesis of the perfume Florol (2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol) via Prins cyclization of isoprenol and isovaraldehyde. Tuning the acidity in a zeolite was done by either incorporating metal centers or changing the initial composition and crystallization time. Furthermore, the interplay among the pore structure, specific mesoporosity, and accessibility of acidic sites is crucial for optimizing Florol synthesis. Strong Brønsted acid sites enhance the formation of the dehydration products, while mild-acidic Brønsted acid sites with a medium strength of accessible acid sites improve the formation of Florol. A maximum Florol yield of ca. 80% was achieved with Al-MFI and Al-FER (only 30 min) with typical nanosheet (nsh) morphology; in addition, values of TOF in the order of 1121 and 2655 h<sup>–1</sup>, respectively, were also achieved. Al-FER-nsh showed itself to be robust, because it can be reused several times without any apparent loss of its catalytic activity. Finally, different green chemistry parameters were also applied to the studied zeolites in the synthesis of Florol, suggesting the high efficiency of the best catalyst (Al-MFI-nsh).","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486432","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 : 2024-10-22DOI: 10.1021/acssuschemeng.4c04497
Tong Zhang, Shubin Li, Lei Chen, Weiwen Zhang, Tao Sun
Cyanobacteria are known to be photoautotrophic cell factories capable of converting CO2 into valuable chemicals. The newly discovered marine cyanobacterium Synechococcus sp. PCC 11901 (hereafter PCC 11901) offers several advantages like rapid growth, high biomass, and high salinity tolerance, representing a promising chassis. To promote its application, we developed genetic toolboxes applicable to PCC 11901 in this study. First, a cobalamin (VB12)-independent chassis was constructed, allowing for cheaper cultivation. Second, genome copy numbers and transformation methods were, respectively, measured and optimized. Then, 14 neutral sites were identified and characterized within the genome PCC 11901, providing locations for genetic integration of exogenous cassettes. Subsequently, promoter libraries were developed, reaching an expression range of approximately 800 folds for constitutive promoters and an induction fold of up to approximately 400 for inducible promotors, respectively. As a proof of concept, natural production of the total lipid and phycocyanin was investigated using VB12-independent chassis, which realized an increase of 14.91% with lipid content compared with that of the wild-type strain. Further, we engineered the synthetic pathways of glucosylglycerol (GG) into PCC 11901 using the established toolboxes, reaching 590.41 ± 21.48 mg/L for GG production and self-sedimentation in photoreactors with the highest OD750 nm at 17.57 ± 0.77. Finally, the GG-producing strain grew well in seawater, reaching 324.50 ± 5.34 mg/L in shaking flask, which provided new strategies for cyanobacteria cultivation and production. Our work here made it possible to develop the fast-growing PCC 11901 as efficient carbon-neutral cell factory in the future.
{"title":"Extended Toolboxes Enable Efficient Biosynthesis of Multiple Products from CO2 in Fast-Growing Synechococcus sp. PCC 11901","authors":"Tong Zhang, Shubin Li, Lei Chen, Weiwen Zhang, Tao Sun","doi":"10.1021/acssuschemeng.4c04497","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04497","url":null,"abstract":"Cyanobacteria are known to be photoautotrophic cell factories capable of converting CO<sub>2</sub> into valuable chemicals. The newly discovered marine cyanobacterium <i>Synechococcus</i> sp. PCC 11901 (hereafter PCC 11901) offers several advantages like rapid growth, high biomass, and high salinity tolerance, representing a promising chassis. To promote its application, we developed genetic toolboxes applicable to PCC 11901 in this study. First, a cobalamin (V<sub>B12</sub>)-independent chassis was constructed, allowing for cheaper cultivation. Second, genome copy numbers and transformation methods were, respectively, measured and optimized. Then, 14 neutral sites were identified and characterized within the genome PCC 11901, providing locations for genetic integration of exogenous cassettes. Subsequently, promoter libraries were developed, reaching an expression range of approximately 800 folds for constitutive promoters and an induction fold of up to approximately 400 for inducible promotors, respectively. As a proof of concept, natural production of the total lipid and phycocyanin was investigated using V<sub>B12</sub>-independent chassis, which realized an increase of 14.91% with lipid content compared with that of the wild-type strain. Further, we engineered the synthetic pathways of glucosylglycerol (GG) into PCC 11901 using the established toolboxes, reaching 590.41 ± 21.48 mg/L for GG production and self-sedimentation in photoreactors with the highest OD<sub>750 nm</sub> at 17.57 ± 0.77. Finally, the GG-producing strain grew well in seawater, reaching 324.50 ± 5.34 mg/L in shaking flask, which provided new strategies for cyanobacteria cultivation and production. Our work here made it possible to develop the fast-growing PCC 11901 as efficient carbon-neutral cell factory in the future.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487101","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}
Access to freshwater is crucial for a sustainable environment and human ecosystems. Hybrid capacitive deionization (HCDI) based on attractive pseudocapacitive reactions is considered a promising environmentally friendly and energy-saving electrochemical desalination technology. However, the application of HCDI technology is still limited, mainly due to the unsatisfactory ion adsorption ability of the pseudocapacitive electrode. Herein, we unveil an innovative redox-active organic molecule (PATD) that showcases outstanding pseudocapacitive properties for electrochemical desalination. Notably, the integration of redox-active C═O and C═N groups in the PATD molecule promotes stable and efficient pseudocapacitive reactions. Additionally, the rigid molecular structure, combined with a minimal HOMO–LUMO energy gap, ensures exceptional redox characteristics and superior electron transfer capability of the PATD molecule, which are substantiated by experimental evidence and theoretical studies. As an electrode, the PATD molecule exhibits significant pseudocapacitive characteristics along with excellent long-term stability, retaining 89.0% of its capacitance after 5000 cycles in a NaCl aqueous solution. In practical applications, the developed HCDI device incorporating the PATD electrode demonstrates a remarkably high salt removal capacity of 56.9 mg g–1, a swift average removal rate of 1.9 mg g–1 min–1, and consistent regeneration performance while attaining reliable energy recovery, which highlights its promising prospects for sustainable desalination technologies.
{"title":"Crafting an Exceptionally Redox-Active Organic Molecule Boasting Superior Electron Mobility for High-Performance Electrochemical Desalination","authors":"Yueheng Tao, Jing Jin, Yujie Cui, Houxiang Wang, Zhangjiashuo Qian, Minjie Shi","doi":"10.1021/acssuschemeng.4c06939","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06939","url":null,"abstract":"Access to freshwater is crucial for a sustainable environment and human ecosystems. Hybrid capacitive deionization (HCDI) based on attractive pseudocapacitive reactions is considered a promising environmentally friendly and energy-saving electrochemical desalination technology. However, the application of HCDI technology is still limited, mainly due to the unsatisfactory ion adsorption ability of the pseudocapacitive electrode. Herein, we unveil an innovative redox-active organic molecule (PATD) that showcases outstanding pseudocapacitive properties for electrochemical desalination. Notably, the integration of redox-active C═O and C═N groups in the PATD molecule promotes stable and efficient pseudocapacitive reactions. Additionally, the rigid molecular structure, combined with a minimal HOMO–LUMO energy gap, ensures exceptional redox characteristics and superior electron transfer capability of the PATD molecule, which are substantiated by experimental evidence and theoretical studies. As an electrode, the PATD molecule exhibits significant pseudocapacitive characteristics along with excellent long-term stability, retaining 89.0% of its capacitance after 5000 cycles in a NaCl aqueous solution. In practical applications, the developed HCDI device incorporating the PATD electrode demonstrates a remarkably high salt removal capacity of 56.9 mg g<sup>–1</sup>, a swift average removal rate of 1.9 mg g<sup>–1</sup> min<sup>–1</sup>, and consistent regeneration performance while attaining reliable energy recovery, which highlights its promising prospects for sustainable desalination technologies.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452076","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 : 2024-10-21DOI: 10.1021/acssuschemeng.4c06486
Yukun Qin, Xiong Qian, Yong Tao, Chuanlin Hu, Fazhou Wang
Waste dolomite powder, a widely available industrial byproduct, has recently gained attention as a potential supplementary cementitious material. However, its inert reactivity challenges its potential for substantial cement replacement. This study explores the effectiveness of partially calcined dolomite (PCD) integrated with calcined clay for a high cement substitution level. A novel partial calcination method is introduced to optimize the decomposition of MgCO3 and CaCO3 to produce a core–shell structure with a highly reactive external CaO/MgO layer and a dense internal core of CaCO3 and MgO. This configuration significantly enhances the formation of calcium silicate hydrate gels and carboaluminate phases, improving the overall strength of the material by over 90% at both 7 and 28 days compared to the sample with uncalcined dolomite. Additionally, the formulation of the proposed materials reduces CO2 emission by 43% and energy consumption by 47% without sacrificing compressive strength. This innovative calcination technique broadens the application of waste dolomite in the development of sustainable cementitious materials.
{"title":"Unlocking the Potential of Dolomite for Developing More Sustainable Cementitious Materials through Partial Calcination","authors":"Yukun Qin, Xiong Qian, Yong Tao, Chuanlin Hu, Fazhou Wang","doi":"10.1021/acssuschemeng.4c06486","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06486","url":null,"abstract":"Waste dolomite powder, a widely available industrial byproduct, has recently gained attention as a potential supplementary cementitious material. However, its inert reactivity challenges its potential for substantial cement replacement. This study explores the effectiveness of partially calcined dolomite (PCD) integrated with calcined clay for a high cement substitution level. A novel partial calcination method is introduced to optimize the decomposition of MgCO<sub>3</sub> and CaCO<sub>3</sub> to produce a core–shell structure with a highly reactive external CaO/MgO layer and a dense internal core of CaCO<sub>3</sub> and MgO. This configuration significantly enhances the formation of calcium silicate hydrate gels and carboaluminate phases, improving the overall strength of the material by over 90% at both 7 and 28 days compared to the sample with uncalcined dolomite. Additionally, the formulation of the proposed materials reduces CO<sub>2</sub> emission by 43% and energy consumption by 47% without sacrificing compressive strength. This innovative calcination technique broadens the application of waste dolomite in the development of sustainable cementitious materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452077","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 : 2024-10-21DOI: 10.1021/acssuschemeng.4c03234
Kwang-Hyun Ryu, Ji-Hyun Cho, Tae-Hyung Lee, Hoon Kim, Gi-Yeon Han, Jong-Ho Back, Hyun-Joong Kim
Previous studies aiming to achieve sustainability in adhesive materials, primarily focused on the integration of bioderived or biodegradable components. However, existing sustainable adhesives often prioritize permanent adhesion over removability, which limits their recyclability. Herein, we introduce an innovative approach for producing scalable, biodegradable, and removable hot-melt adhesives, offering sustainability. Polybutylene succinate (PBS) was selected as the base polymer because of its excellent melt processability, biodegradability, and commercial availability. To impart adhesiveness, three biomass-derived tackifiers were incorporated; basic rosin, disproportionated rosin, and rosin ester. The use of a twin-screw extruder enabled the efficient mixing of the base polymer and tackifiers for large-scale production at the kilogram scale. Our investigation revealed that basic rosin exhibited optimal compatibility and wettability, which were attributed to its high acid value. The high acid value promoted rapid crystallization and minimized crystal defects. A correlation between the crystallization behavior and adhesion strength was also established, identifying the optimal composition. The optimal composition yields a satisfactory adhesion strength (2.5 N/25 mm) that makes it suitable for removable or repositionable adhesives. Additionally, our optimized adhesive exhibited sufficient biodegradability and was completely decomposed by lipase within 21 d, which has not been observed in previous sustainable hot-melt adhesive studies. This study provides a practical pathway for enhancing adhesive sustainability with the potential for further advancements in tailoring the adhesion strength for diverse applications in future research.
{"title":"Toward Sustainable Adhesives with Biodegradability, Scalability, and Removability: Poly(butylene succinate)-Based Hot-Melt Adhesives","authors":"Kwang-Hyun Ryu, Ji-Hyun Cho, Tae-Hyung Lee, Hoon Kim, Gi-Yeon Han, Jong-Ho Back, Hyun-Joong Kim","doi":"10.1021/acssuschemeng.4c03234","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c03234","url":null,"abstract":"Previous studies aiming to achieve sustainability in adhesive materials, primarily focused on the integration of bioderived or biodegradable components. However, existing sustainable adhesives often prioritize permanent adhesion over removability, which limits their recyclability. Herein, we introduce an innovative approach for producing scalable, biodegradable, and removable hot-melt adhesives, offering sustainability. Polybutylene succinate (PBS) was selected as the base polymer because of its excellent melt processability, biodegradability, and commercial availability. To impart adhesiveness, three biomass-derived tackifiers were incorporated; basic rosin, disproportionated rosin, and rosin ester. The use of a twin-screw extruder enabled the efficient mixing of the base polymer and tackifiers for large-scale production at the kilogram scale. Our investigation revealed that basic rosin exhibited optimal compatibility and wettability, which were attributed to its high acid value. The high acid value promoted rapid crystallization and minimized crystal defects. A correlation between the crystallization behavior and adhesion strength was also established, identifying the optimal composition. The optimal composition yields a satisfactory adhesion strength (2.5 N/25 mm) that makes it suitable for removable or repositionable adhesives. Additionally, our optimized adhesive exhibited sufficient biodegradability and was completely decomposed by lipase within 21 d, which has not been observed in previous sustainable hot-melt adhesive studies. This study provides a practical pathway for enhancing adhesive sustainability with the potential for further advancements in tailoring the adhesion strength for diverse applications in future research.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452006","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 : 2024-10-21DOI: 10.1021/acssuschemeng.4c05353
Jimin Park, Caria Evans, Jacob Maier, Marta Hatzell, Stefan France, Carsten Sievers, Andreas S. Bommarius
Three potential routes for paracetamol synthesis from renewable phenol feedstock were examined and compared to each other and existing industrial routes with respect to Green Chemistry metrics and industrial viability. The routes tested were the acetamidation of hydroquinone, the imination and reduction of benzoquinone, and the hydrogenation of 4-nitrophenol. The hydroquinone and benzoquinone routes suffered from poor conversion and selectivity. The 4-nitrophenol route achieved good conversion, yield, and Green Chemistry metrics and is the most industrially viable of the three routes. When compared to existing routes, the 4-nitrophenol route is comparable or superior in terms of reactor metrics, Green Chemistry considerations, and raw material costs.
{"title":"Renewables-Based Routes to Paracetamol: A Green Chemistry Analysis","authors":"Jimin Park, Caria Evans, Jacob Maier, Marta Hatzell, Stefan France, Carsten Sievers, Andreas S. Bommarius","doi":"10.1021/acssuschemeng.4c05353","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05353","url":null,"abstract":"Three potential routes for paracetamol synthesis from renewable phenol feedstock were examined and compared to each other and existing industrial routes with respect to Green Chemistry metrics and industrial viability. The routes tested were the acetamidation of hydroquinone, the imination and reduction of benzoquinone, and the hydrogenation of 4-nitrophenol. The hydroquinone and benzoquinone routes suffered from poor conversion and selectivity. The 4-nitrophenol route achieved good conversion, yield, and Green Chemistry metrics and is the most industrially viable of the three routes. When compared to existing routes, the 4-nitrophenol route is comparable or superior in terms of reactor metrics, Green Chemistry considerations, and raw material costs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452007","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}
A new and effective protocol driven by visible light has been introduced for the first time to synthesize 2-benzoxazolecarboxamides from benzoxazinones and amines in the presence of a conjugated microporous polymer, PATP. The reaction produced a variety of 2-benzoxazolecarboxamides in moderate to good yields while demonstrating excellent functional group tolerance under mild conditions. In comparison with transition metal complexes or organic dye molecules, PATP exhibited superior catalytic activity due to its extended π-conjugation system, porous structure, and electronic donor–acceptor (D-A) characteristics. Moreover, the polymer PATP showed consistent recyclability without any significant loss of photocatalytic efficiency after recovery.
{"title":"Visible Light Induced Synthesis of 2-Benzoxazolecarboxamides Promoted by a Conjugated Microporous Polymer","authors":"Yujie Zhang, Rui Wang, Cuifen Lu, Chao Ma, Feiyi Wang, Guichun Yang, Yuexing Zhang, Junqi Nie","doi":"10.1021/acssuschemeng.4c05275","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05275","url":null,"abstract":"A new and effective protocol driven by visible light has been introduced for the first time to synthesize 2-benzoxazolecarboxamides from benzoxazinones and amines in the presence of a conjugated microporous polymer, PATP. The reaction produced a variety of 2-benzoxazolecarboxamides in moderate to good yields while demonstrating excellent functional group tolerance under mild conditions. In comparison with transition metal complexes or organic dye molecules, PATP exhibited superior catalytic activity due to its extended π-conjugation system, porous structure, and electronic donor–acceptor (D-A) characteristics. Moreover, the polymer PATP showed consistent recyclability without any significant loss of photocatalytic efficiency after recovery.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452012","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 : 2024-10-21DOI: 10.1021/acssuschemeng.4c05394
Cini M. Suresh, Mrityunjay K. Jha, Navneet, Hemant K. Kashyap, Pravin Popinand Ingole
The conventional CO2 capture and utilization (CCU) uses aqueous amine solutions, but its environmental hostility and energy-intensive process to regenerate CO2 are major hurdles toward sustainability. Alternatively, electrochemical reactive CO2 capture (eRCC) that integrates CO2 capture and its conversion has been considered a promising method for economical and sustainable CO2 valorization. However, designing a suitable electrolyte system with tailored electrochemical interfaces for efficient eRCC is a major challenge. Herein, we report a tailored deep eutectic solvent (DES)-based electrolyte containing a superbase (DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene), an aprotic diluent (DMSO: dimethyl sulfoxide), and ethaline (Eth) for an efficient and low-cost eRCC. The tailored DES electrolyte depicts multifold improvement in eRCC performance compared to pristine Eth with good CO2 capture capacity and a superior conversion rate (363.6 μmol cm–2 h–1) at elevated temperatures (i.e., 50 °C). The spectroscopic, electrochemical, and theoretical (AIMD) investigations suggest that the modulated molecular interactions between DES and CO2 boost its capture and facilitate the release of captured CO2 for subsequent reduction. Overall, the facile mass transport, higher concentration of CO2 at the electrode surface, and greater stabilization of intermediates due to the formation of a compact electrical double layer in a tailored DES resulted in relatively high eRCC performance.
传统的二氧化碳捕获和利用（CCU）使用胺水溶液，但其对环境的不利影响和再生二氧化碳的高能耗过程是实现可持续发展的主要障碍。作为替代方案，电化学反应式二氧化碳捕集（eRCC）将二氧化碳捕集与转化融为一体，被认为是一种经济、可持续的二氧化碳增值方法。然而，设计一个具有定制电化学界面的合适电解质系统以实现高效的 eRCC 是一项重大挑战。在此，我们报告了一种基于深共晶溶剂（DES）的定制电解质，它含有一种超碱基（DBU：1,8-二氮杂双环[5.4.0]十一碳-7-烯）、一种非烷基稀释剂（DMSO：二甲亚砜）和乙碱（Eth），可用于高效、低成本的 eRCC。与原始乙醇相比，定制的 DES 电解质的 eRCC 性能提高了数倍，具有良好的二氧化碳捕获能力，在高温（即 50 °C）条件下转化率更高（363.6 μmol cm-2 h-1）。光谱、电化学和理论（AIMD）研究表明，DES 与 CO2 之间的调制分子相互作用促进了对 CO2 的捕获，并有助于释放捕获的 CO2 以进行后续还原。总之，由于在定制的 DES 中形成了紧凑的电双层，因此质量传输方便，电极表面的二氧化碳浓度更高，中间产物更加稳定，从而实现了相对较高的 eRCC 性能。
{"title":"Modulating Molecular Interactions in Bulk and Electrochemical Interfaces of Deep Eutectic Solvent-Based Tailored Electrolytes for Facilitating Reactive CO2 Capture","authors":"Cini M. Suresh, Mrityunjay K. Jha, Navneet, Hemant K. Kashyap, Pravin Popinand Ingole","doi":"10.1021/acssuschemeng.4c05394","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05394","url":null,"abstract":"The conventional CO<sub>2</sub> capture and utilization (CCU) uses aqueous amine solutions, but its environmental hostility and energy-intensive process to regenerate CO<sub>2</sub> are major hurdles toward sustainability. Alternatively, electrochemical reactive CO<sub>2</sub> capture (eRCC) that integrates CO<sub>2</sub> capture and its conversion has been considered a promising method for economical and sustainable CO<sub>2</sub> valorization. However, designing a suitable electrolyte system with tailored electrochemical interfaces for efficient eRCC is a major challenge. Herein, we report a tailored deep eutectic solvent (DES)-based electrolyte containing a superbase (DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene), an aprotic diluent (DMSO: dimethyl sulfoxide), and ethaline (Eth) for an efficient and low-cost eRCC. The tailored DES electrolyte depicts multifold improvement in eRCC performance compared to pristine Eth with good CO<sub>2</sub> capture capacity and a superior conversion rate (363.6 μmol cm<sup>–2</sup> h<sup>–1</sup>) at elevated temperatures (i.e., 50 °C). The spectroscopic, electrochemical, and theoretical (AIMD) investigations suggest that the modulated molecular interactions between DES and CO<sub>2</sub> boost its capture and facilitate the release of captured CO<sub>2</sub> for subsequent reduction. Overall, the facile mass transport, higher concentration of CO<sub>2</sub> at the electrode surface, and greater stabilization of intermediates due to the formation of a compact electrical double layer in a tailored DES resulted in relatively high eRCC performance.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452074","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 : 2024-10-20DOI: 10.1021/acssuschemeng.4c05654
Mahima Gupta, Vaibhav Pramod Charpe, Kuo Chu Hwang
We have developed a singlet oxygen (1O2)-mediated regioselective thiocyanation of terminal alkynes, indoles, pyrrole, anilines, and phenols using ammonium thiocyanate (NH4SCN) as an SCN source under visible light irradiation at room temperature. The oxidative thiocyanation of terminal alkynes forms α-keto thiocyanates, while indoles, pyrrole, anilines, and phenols regioselectively form the respective thiocyanate products. Herein, thiocyanate (SCN anion) undergoes single electron transfer (SET) by transferring an electron to singlet oxygen and forms an •SCN radical, which readily reacts with substrates to form thiocyanate products. Green chemistry metrics and Eco-scale evaluations signify that the current oxidative and regioselective thiocyanation protocol is an acceptable green organic synthesis process. Moreover, this method requires a simple reaction setup and uses inexpensive NH4SCN as an SCN source, O2 as an oxidant, and low-energy visible light. Thus, the current oxidative thiocyanation process is mild, green, highly efficient, eco-friendly, and environmentally feasible.
{"title":"Singlet Oxygen-Mediated Regioselective Thiocyanation of Terminal Alkynes, Alkenes, Indoles, Pyrrole, Anilines, and Phenols","authors":"Mahima Gupta, Vaibhav Pramod Charpe, Kuo Chu Hwang","doi":"10.1021/acssuschemeng.4c05654","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05654","url":null,"abstract":"We have developed a singlet oxygen (<sup>1</sup>O<sub>2</sub>)-mediated regioselective thiocyanation of terminal alkynes, indoles, pyrrole, anilines, and phenols using ammonium thiocyanate (NH<sub>4</sub>SCN) as an SCN source under visible light irradiation at room temperature. The oxidative thiocyanation of terminal alkynes forms α-keto thiocyanates, while indoles, pyrrole, anilines, and phenols regioselectively form the respective thiocyanate products. Herein, thiocyanate (SCN anion) undergoes single electron transfer (SET) by transferring an electron to singlet oxygen and forms an <sup>•</sup>SCN radical, which readily reacts with substrates to form thiocyanate products. Green chemistry metrics and Eco-scale evaluations signify that the current oxidative and regioselective thiocyanation protocol is an acceptable green organic synthesis process. Moreover, this method requires a simple reaction setup and uses inexpensive NH<sub>4</sub>SCN as an SCN source, O<sub>2</sub> as an oxidant, and low-energy visible light. Thus, the current oxidative thiocyanation process is mild, green, highly efficient, eco-friendly, and environmentally feasible.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451654","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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