Pub Date : 2024-12-31DOI: 10.1021/acssuschemeng.4c06345
Xinge Miao, Pengxin Yu, Mingzhi Du, Yongsheng Yuan, Jianyu Han, Jingen Long, Lingzhao Kong, Junju Mu, Weiran Yang
Herein, a new method to selectively convert tartaric acid to succinic acid was developed by catalytic transfer hydrogenation using iodine as the catalyst and methyl isobutyl ketone (MIBK) as both the hydrogen donor and the solvent. Under optimized reaction conditions, 85% succinic acid can be obtained directly from tartaric acid with a catalytic amount of iodine in MIBK at 160 °C for 4 h. Moreover, succinic acid can automatically precipitate out from the reaction solvent after cooling due to its much lower solubility in MIBK at room temperature, which provides an easy way for product separation. The detailed mechanism has been studied extensively by control experiments. The cheap catalyst, mild reaction condition, and easy separation of the product make this process a green path for succinic acid production.
{"title":"Production of Succinic Acid Directly from Tartaric Acid by Iodine-Mediated Transfer Hydrogenation","authors":"Xinge Miao, Pengxin Yu, Mingzhi Du, Yongsheng Yuan, Jianyu Han, Jingen Long, Lingzhao Kong, Junju Mu, Weiran Yang","doi":"10.1021/acssuschemeng.4c06345","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06345","url":null,"abstract":"Herein, a new method to selectively convert tartaric acid to succinic acid was developed by catalytic transfer hydrogenation using iodine as the catalyst and methyl isobutyl ketone (MIBK) as both the hydrogen donor and the solvent. Under optimized reaction conditions, 85% succinic acid can be obtained directly from tartaric acid with a catalytic amount of iodine in MIBK at 160 °C for 4 h. Moreover, succinic acid can automatically precipitate out from the reaction solvent after cooling due to its much lower solubility in MIBK at room temperature, which provides an easy way for product separation. The detailed mechanism has been studied extensively by control experiments. The cheap catalyst, mild reaction condition, and easy separation of the product make this process a green path for succinic acid production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142908288","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 : 2024-12-31DOI: 10.1021/acssuschemeng.4c06155
Shilong Liu, Gege Pan, MiaoMiao Wei, Baoyan Zhi, Yanchang Zhang, Chengjun Hu, Hao Li
Cyclohexanone, a product of phenol hydrogenation, is a very reactive intermediate, which can easily generate byproducts such as cyclohexanol and cyclohexane, and there is a difficult-to-regulate “seesaw effect”. In this paper, a defective catalyst, Pd/Nb2O5-800-AP, was synthesized by the hydrothermal method at 170 °C and 1 MPa H2, aiming to break the difficult equilibrium between the high conversion of phenol and the high selectivity of cyclohexanone, which has a good industrial prospect. By changing the calcination temperature of the carrier to control the surface defect content, Pd was placed in an electron-rich state, which promoted the activation of hydrogen molecules and adsorption of phenol in a “nonplanar” manner, which was favorable for the generation of cyclohexanone as a product. In addition, the formation of electron-deficient oxygen defects and low-valent Nb4+ on the surface of the AP-treated catalysts promoted the adsorption and activation of oxygen-containing functional groups, which enhanced the activity of the phenol HDO reaction.
{"title":"Preparation of Defective Niobium-Based Catalysts to Address the “Seesaw Effect” in Phenol Hydrodeoxygenation","authors":"Shilong Liu, Gege Pan, MiaoMiao Wei, Baoyan Zhi, Yanchang Zhang, Chengjun Hu, Hao Li","doi":"10.1021/acssuschemeng.4c06155","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06155","url":null,"abstract":"Cyclohexanone, a product of phenol hydrogenation, is a very reactive intermediate, which can easily generate byproducts such as cyclohexanol and cyclohexane, and there is a difficult-to-regulate “seesaw effect”. In this paper, a defective catalyst, Pd/Nb<sub>2</sub>O<sub>5</sub>-800-AP, was synthesized by the hydrothermal method at 170 °C and 1 MPa H<sub>2</sub>, aiming to break the difficult equilibrium between the high conversion of phenol and the high selectivity of cyclohexanone, which has a good industrial prospect. By changing the calcination temperature of the carrier to control the surface defect content, Pd was placed in an electron-rich state, which promoted the activation of hydrogen molecules and adsorption of phenol in a “nonplanar” manner, which was favorable for the generation of cyclohexanone as a product. In addition, the formation of electron-deficient oxygen defects and low-valent Nb<sup>4+</sup> on the surface of the AP-treated catalysts promoted the adsorption and activation of oxygen-containing functional groups, which enhanced the activity of the phenol HDO reaction.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142908287","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}
It is well recognized in recent studies that water molecules at the gas–liquid interface of microdroplets spontaneously dissociate into hydronium and hydroxide and form superacids/superbases and reactive species (hydrated electrons, hydroxide radicals, hydrogen peroxide, water radical cations/anions, etc.) due to the 109 V m–1 electric field. In contrast to extensive interest in spontaneous redox reactions by the reactive species in microdroplet studies, limited attention has been attracted by gram-scale organic synthesis catalyzed by the spontaneously formed superacids/superbases. This study demonstrates spontaneous organic catalysis of the superacids for Paal–Knorr reactions, one of the most classic pathways to construct N-substituted pyrroles with biologically and pharmaceutically important roles. Paal–Knorr reactions can proceed well with no external catalysts in isopropanol microdroplets within 10 min at room temperature. Sixteen N-substituted pyrroles were synthesized using the microdroplet method with 83–99% yields, several orders of magnitude reaction acceleration (a typical rate acceleration factor of 1.18 × 103 based on the ratio of the rate constants), and a scale-up rate of 5.50 g h–1. By avoiding external catalysts, thermal irradiation, long reaction times, and problematic solvents required by conventional Paal–Knorr methods, the microdroplet method was a green, efficient, and attractive alternative for the construction of pyrroles and their derivatives.
{"title":"Spontaneous Catalytic Paal–Knorr Reactions for N-Substituted Pyrrole Synthesis by Microdroplet Chemistry","authors":"Jiayao Li, Jiannan Sun, Yizhou Wang, Jinhua Liu, Heyong Cheng","doi":"10.1021/acssuschemeng.4c08638","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08638","url":null,"abstract":"It is well recognized in recent studies that water molecules at the gas–liquid interface of microdroplets spontaneously dissociate into hydronium and hydroxide and form superacids/superbases and reactive species (hydrated electrons, hydroxide radicals, hydrogen peroxide, water radical cations/anions, etc.) due to the 10<sup>9</sup> V m<sup>–1</sup> electric field. In contrast to extensive interest in spontaneous redox reactions by the reactive species in microdroplet studies, limited attention has been attracted by gram-scale organic synthesis catalyzed by the spontaneously formed superacids/superbases. This study demonstrates spontaneous organic catalysis of the superacids for Paal–Knorr reactions, one of the most classic pathways to construct <i>N</i>-substituted pyrroles with biologically and pharmaceutically important roles. Paal–Knorr reactions can proceed well with no external catalysts in isopropanol microdroplets within 10 min at room temperature. Sixteen <i>N</i>-substituted pyrroles were synthesized using the microdroplet method with 83–99% yields, several orders of magnitude reaction acceleration (a typical rate acceleration factor of 1.18 × 10<sup>3</sup> based on the ratio of the rate constants), and a scale-up rate of 5.50 g h<sup>–1</sup>. By avoiding external catalysts, thermal irradiation, long reaction times, and problematic solvents required by conventional Paal–Knorr methods, the microdroplet method was a green, efficient, and attractive alternative for the construction of pyrroles and their derivatives.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142908290","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 : 2024-12-30DOI: 10.1021/acssuschemeng.4c05655
Bo Li, Xiao Yu, Zhongjian Tian, Yuqin Jiang, Tengfei Niu
Using H2O2 for oxidative cleavage of renewable unsaturated fatty acids (UFA) or plant oil is a green method for preparing biobased mono- and dicarboxylic acids. However, due to the insolubility of UFA or oil in water, organic solvents or unrecyclable surfactants are usually needed to promote the contact between substrates and H2O2, which does not meet the Sustainable Development Goals. In this work, a series of lignin quaternary ammonium-supported phosphotungstate catalysts has been designed and prepared. Among these catalysts, HPW-AL6500-QAS16 showed the best catalytic activity for the oxidative cleavage of oleic acid (OA) and soybean oil (SBO) using H2O2 as the oxidant without a solvent and additive. This lignin-based catalyst afforded 100% OA and SBO conversion and up to 96.2% azelaic acid (AA), 94.6% nonanoic acid (NA) selectivities for OA and 91.8% AA, and 85.2% NA selectivities for SBO. More importantly, the lignin-based catalyst could be easily recovered and reused at least 5 times without a significant loss in its catalytic activity. These characteristics make the oxidative cleavage of OA and SBO more efficient and environmentally friendly, which may be beneficial for industry applications.
利用 H2O2 氧化裂解可再生不饱和脂肪酸（UFA）或植物油是制备生物基单羧酸和二羧酸的一种绿色方法。然而，由于 UFA 或油不溶于水，通常需要使用有机溶剂或不可回收的表面活性剂来促进底物与 H2O2 的接触，这不符合可持续发展目标。本研究设计并制备了一系列木质素季铵支撑的磷钨酸盐催化剂。在这些催化剂中，HPW-AL6500-QAS16 以 H2O2 为氧化剂，在不使用溶剂和添加剂的情况下，对油酸（OA）和大豆油（SBO）的氧化裂解表现出最佳的催化活性。这种木质素基催化剂可实现 100% 的 OA 和 SBO 转化率，对 OA 的壬二酸（AA）选择性高达 96.2%，对 SBO 的 AA 选择性高达 91.8%，对 NA 的选择性高达 85.2%。更重要的是，这种基于木质素的催化剂可以很容易地回收并重复使用至少 5 次，而其催化活性不会明显降低。这些特点使得 OA 和 SBO 的氧化裂解更加高效和环保，有利于工业应用。
{"title":"Lignin Quaternary Ammonium Phosphotungstate as a Recycle Catalyst for Oxidative Cleavage of Unsaturated Fatty Acids and Soybean Oil","authors":"Bo Li, Xiao Yu, Zhongjian Tian, Yuqin Jiang, Tengfei Niu","doi":"10.1021/acssuschemeng.4c05655","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05655","url":null,"abstract":"Using H<sub>2</sub>O<sub>2</sub> for oxidative cleavage of renewable unsaturated fatty acids (UFA) or plant oil is a green method for preparing biobased mono- and dicarboxylic acids. However, due to the insolubility of UFA or oil in water, organic solvents or unrecyclable surfactants are usually needed to promote the contact between substrates and H<sub>2</sub>O<sub>2</sub>, which does not meet the Sustainable Development Goals. In this work, a series of lignin quaternary ammonium-supported phosphotungstate catalysts has been designed and prepared. Among these catalysts, HPW-AL<sub>6500</sub>-QAS<sub>16</sub> showed the best catalytic activity for the oxidative cleavage of oleic acid (OA) and soybean oil (SBO) using H<sub>2</sub>O<sub>2</sub> as the oxidant without a solvent and additive. This lignin-based catalyst afforded 100% OA and SBO conversion and up to 96.2% azelaic acid (AA), 94.6% nonanoic acid (NA) selectivities for OA and 91.8% AA, and 85.2% NA selectivities for SBO. More importantly, the lignin-based catalyst could be easily recovered and reused at least 5 times without a significant loss in its catalytic activity. These characteristics make the oxidative cleavage of OA and SBO more efficient and environmentally friendly, which may be beneficial for industry applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905348","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}
To effectively mitigate the global warming problem caused by excessive CO2 emissions, the implementation of direct air capture (DAC) technology has emerged as one of the most promising strategies for capturing CO2 from the atmosphere. The key to DAC technology hinges on the development of high-performance solid sorbent materials that demonstrate high CO2 adsorption capacity and gas separation selectivity, particularly under low CO2 partial pressure conditions. Herein, we have successfully developed a class of MOF@carboxylated wood sponge (MOF@CWS) hybrid sorbents, capable of efficient CO2 capture from low-concentration (less than 10,000 ppm) CO2 sources, achieved by embedding the porous MOF into carboxylated wood sponges (CWS) substrate via an in situ growth route. Within the MOF@CWS series, the CO2 uptake capacity of Mg-MOF-74@CWS is 3.61 and 2.65 mmol/g at 1 bar, 273 and 298 K, respectively, significantly higher than those of CWS and HKUST-1@CWS. Moreover, this material exhibited outstanding DAC performance, with the CO2 sorption capacity at 273 K up to 0.56 mmol/g from ambient air (ca. 400 ppm of CO2), surpassing most other solid sorbents. The obtained Mg-MOF-74@CWS also demonstrated exceptional CO2/CH4 separation performance, primarily due to the unique pore structure and augmented interaction between the CO2 molecules and the hybrid sorbents. The results of this study indicate that Mg-MOF-74@CWS has potential as an efficient solid sorbent for the DAC of CO2.
{"title":"Supporting Porous Metal–Organic Frameworks on Carboxylated-Wood Sponges for Direct Air Capture and Highly Selective CO2/CH4 Separation","authors":"Xupeng Zhang, Kaiqian Li, Longxin Guo, Zhiping Xu, Shuduan Deng, Ying Liu, Gang Zhu","doi":"10.1021/acssuschemeng.4c05232","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05232","url":null,"abstract":"To effectively mitigate the global warming problem caused by excessive CO<sub>2</sub> emissions, the implementation of direct air capture (DAC) technology has emerged as one of the most promising strategies for capturing CO<sub>2</sub> from the atmosphere. The key to DAC technology hinges on the development of high-performance solid sorbent materials that demonstrate high CO<sub>2</sub> adsorption capacity and gas separation selectivity, particularly under low CO<sub>2</sub> partial pressure conditions. Herein, we have successfully developed a class of MOF@carboxylated wood sponge (MOF@CWS) hybrid sorbents, capable of efficient CO<sub>2</sub> capture from low-concentration (less than 10,000 ppm) CO<sub>2</sub> sources, achieved by embedding the porous MOF into carboxylated wood sponges (CWS) substrate via an in situ growth route. Within the MOF@CWS series, the CO<sub>2</sub> uptake capacity of Mg-MOF-74@CWS is 3.61 and 2.65 mmol/g at 1 bar, 273 and 298 K, respectively, significantly higher than those of CWS and HKUST-1@CWS. Moreover, this material exhibited outstanding DAC performance, with the CO<sub>2</sub> sorption capacity at 273 K up to 0.56 mmol/g from ambient air (ca. 400 ppm of CO<sub>2</sub>), surpassing most other solid sorbents. The obtained Mg-MOF-74@CWS also demonstrated exceptional CO<sub>2</sub>/CH<sub>4</sub> separation performance, primarily due to the unique pore structure and augmented interaction between the CO<sub>2</sub> molecules and the hybrid sorbents. The results of this study indicate that Mg-MOF-74@CWS has potential as an efficient solid sorbent for the DAC of CO<sub>2</sub>.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"344 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905347","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 : 2024-12-26DOI: 10.1021/acssuschemeng.4c07276
Zirui Wu, Tieyu Hu, Zihui Fan, Yongying Wang, Yi Li, Juan Yang
Iron- and nitrogen-codoped carbon (Fe–N–C) catalysts with Fe–N4 active sites offer a promising alternative to noble metal-based materials for the oxygen reduction reaction (ORR), which is essential for energy storage and conversion in applications such as fuel cells and metal–air batteries. This study presents a straightforward and scalable method to synthesize an efficient ORR electrocatalyst that consists of nitrogen-doped carbon and a high density of atomically dispersed single iron atoms, created through the pyrolysis of Fe-zeolitic imidazolate framework (Fe-ZIF-8) precursors. The Fe-ZIF-8 framework effectively restricts the migration and agglomeration of iron species, resulting in obtained Fe–N–C with conductive, mesoporous carbon structures and abundant Fe–N4 sites. This structure provides excellent electrocatalytic activity for the ORR, demonstrated by a positive onset potential of 0.985 V vs RHE and a half-wave potential of 0.905 V vs the reversible hydrogen electrode (RHE) in alkaline media, outperforming commercial Pt/C. Additionally, when used as the cathode in a zinc–air battery, the Fe–N–C catalyst delivers high maximum power densities of 170.1 mW cm–2, showcasing its potential for practical energy storage applications.
{"title":"Enhancing Oxygen Reduction Reaction Performance Through Abundant Single Fe Atoms for Advanced Zinc–Air Batteries","authors":"Zirui Wu, Tieyu Hu, Zihui Fan, Yongying Wang, Yi Li, Juan Yang","doi":"10.1021/acssuschemeng.4c07276","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07276","url":null,"abstract":"Iron- and nitrogen-codoped carbon (Fe–N–C) catalysts with Fe–N<sub>4</sub> active sites offer a promising alternative to noble metal-based materials for the oxygen reduction reaction (ORR), which is essential for energy storage and conversion in applications such as fuel cells and metal–air batteries. This study presents a straightforward and scalable method to synthesize an efficient ORR electrocatalyst that consists of nitrogen-doped carbon and a high density of atomically dispersed single iron atoms, created through the pyrolysis of Fe-zeolitic imidazolate framework (Fe-ZIF-8) precursors. The Fe-ZIF-8 framework effectively restricts the migration and agglomeration of iron species, resulting in obtained Fe–N–C with conductive, mesoporous carbon structures and abundant Fe–N<sub>4</sub> sites. This structure provides excellent electrocatalytic activity for the ORR, demonstrated by a positive onset potential of 0.985 V vs RHE and a half-wave potential of 0.905 V vs the reversible hydrogen electrode (RHE) in alkaline media, outperforming commercial Pt/C. Additionally, when used as the cathode in a zinc–air battery, the Fe–N–C catalyst delivers high maximum power densities of 170.1 mW cm<sup>–2</sup>, showcasing its potential for practical energy storage applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886781","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 : 2024-12-25DOI: 10.1021/acssuschemeng.4c08670
Ming Liu, Huimin Li, Bin Zhang, Yanzi Lei, Luyao Luo, Hai Wang
Revealing the relations between the physical and chemical properties of carbon materials with defined composition and structure is an important topic. However, traditional organic carbon precursor-derived carbon materials lack effective fine-tuning methods due to the uncontrollable temperature changes. Herein, a novel strategy termed a “molten salt liquid seal” is introduced to address this issue. Impressively, the uppermost KBr layer in the provided configuration effectively contains the release of carbon organic precursor at low temperatures and forms a protective barrier at high temperatures, thereby inhibiting the oxidation of carbon materials in air. Furthermore, we propose a corresponding “liquid seal” mechanism by monitoring the temperature-dependent morphological evolution of molten salts and carbon materials. Remarkably, the heteroatoms, defects, etc., in the carbon material can be precisely controlled within the range of 100 °C and 0.5 h per interval. Moreover, the carbonization yield is close to or even higher than that of the conventional process under an Ar atmosphere. We also validate the advantages of the resultant carbon materials as anodes in sodium-ion batteries. This innovative approach not only minimizes the reliance of inert atmospheres but also enables the high-yield fabrication of carbon materials in air, significantly advancing the field toward more sustainable practices.
{"title":"Scalable Preparation and Precise Control of Carbon Materials via Molten Salt Liquid Seal Strategy in Air","authors":"Ming Liu, Huimin Li, Bin Zhang, Yanzi Lei, Luyao Luo, Hai Wang","doi":"10.1021/acssuschemeng.4c08670","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08670","url":null,"abstract":"Revealing the relations between the physical and chemical properties of carbon materials with defined composition and structure is an important topic. However, traditional organic carbon precursor-derived carbon materials lack effective fine-tuning methods due to the uncontrollable temperature changes. Herein, a novel strategy termed a “molten salt liquid seal” is introduced to address this issue. Impressively, the uppermost KBr layer in the provided configuration effectively contains the release of carbon organic precursor at low temperatures and forms a protective barrier at high temperatures, thereby inhibiting the oxidation of carbon materials in air. Furthermore, we propose a corresponding “liquid seal” mechanism by monitoring the temperature-dependent morphological evolution of molten salts and carbon materials. Remarkably, the heteroatoms, defects, etc., in the carbon material can be precisely controlled within the range of 100 °C and 0.5 h per interval. Moreover, the carbonization yield is close to or even higher than that of the conventional process under an Ar atmosphere. We also validate the advantages of the resultant carbon materials as anodes in sodium-ion batteries. This innovative approach not only minimizes the reliance of inert atmospheres but also enables the high-yield fabrication of carbon materials in air, significantly advancing the field toward more sustainable practices.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"65 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886782","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 : 2024-12-24DOI: 10.1021/acssuschemeng.4c08069
Runhao Zheng, Liqiang Zhang, Liucheng Wang, Changhe Du, Kunpeng Li, Shoukui Gao, Linxu Fang, Qiang Wang, Daoai Wang
Liquid lubricants can reduce the friction and wear of two relative moving surfaces. However, there are still great challenges to achieve anticreep and superlubricity of liquid lubricants at the same time. In this study, a novel semisolid lubricant (P30SSA) was designed by fixing poly-α-olefins 30 (PAO30) base oil in a three-dimensional network structure constructed by subnanowires (SNW) and stearic acid (SA), avoiding the creep problem of base oil and achieving ultralow friction (0.006–0009) at steel/polytetrafluoroethylene (PTFE) interfaces in a short period (∼6 s). Compared with dry friction, the wear rate of the PTFE was reduced by 98%. Moreover, the friction coefficient remains below 0.01 after more than 150,000 cycles. The ultralow friction behavior is attributed to the increasing bearing ability caused by the three-dimensional network structure in P30SSA, the reduced internal friction of P30SSA generated by the shear thinning of the lubricant during the friction process, and the physisorption film formed on the surface of friction pairs. The P30SSA solves the problem of liquid lubricant creeping and achieves ultralow friction on the surface of steel/PTFE. This work opens up a new direction for semisolid lubricants and provides a new idea for the study of the ultralow friction mechanism.
{"title":"Oil-Based Fast Ultralow Friction Achieved by Semisolid Lubricant Domained by Poly-α-Olefins-Subnanowire–Stearic Acid at Steel/PTFE Interface","authors":"Runhao Zheng, Liqiang Zhang, Liucheng Wang, Changhe Du, Kunpeng Li, Shoukui Gao, Linxu Fang, Qiang Wang, Daoai Wang","doi":"10.1021/acssuschemeng.4c08069","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08069","url":null,"abstract":"Liquid lubricants can reduce the friction and wear of two relative moving surfaces. However, there are still great challenges to achieve anticreep and superlubricity of liquid lubricants at the same time. In this study, a novel semisolid lubricant (P<sub>30</sub>SSA) was designed by fixing poly-α-olefins 30 (PAO30) base oil in a three-dimensional network structure constructed by subnanowires (SNW) and stearic acid (SA), avoiding the creep problem of base oil and achieving ultralow friction (0.006–0009) at steel/polytetrafluoroethylene (PTFE) interfaces in a short period (∼6 s). Compared with dry friction, the wear rate of the PTFE was reduced by 98%. Moreover, the friction coefficient remains below 0.01 after more than 150,000 cycles. The ultralow friction behavior is attributed to the increasing bearing ability caused by the three-dimensional network structure in P<sub>30</sub>SSA, the reduced internal friction of P<sub>30</sub>SSA generated by the shear thinning of the lubricant during the friction process, and the physisorption film formed on the surface of friction pairs. The P<sub>30</sub>SSA solves the problem of liquid lubricant creeping and achieves ultralow friction on the surface of steel/PTFE. This work opens up a new direction for semisolid lubricants and provides a new idea for the study of the ultralow friction mechanism.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880255","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 : 2024-12-23DOI: 10.1021/acssuschemeng.4c08368
Parvin Holakooei, Federica Valentini, Luigi Vaccaro
The unsustainable exploitation of fossil feedstocks for energy and chemical production has led, in the past few years, to the modern energy and environmental crisis, thus stimulating increased awareness in the definition of more sustainable alternatives. Among the transformations of biomass-derived levulinic acid, recognized as one of the top 10 platform molecules, the production of 5-methylpyrrolidinones is of great importance in diverse industrial fields. In this work, we defined a waste-minimized protocol for the production of N-aryl 5-methylpyrrolidinones, aiming both at the synergistic employment of a benign H-source and reaction media and at the optimization of the workup and purification step. The choice of formic acid as the hydrogen carrier and water as the solvent was beneficial for the replacement of gaseous hydrogen typically used in the synthesis of N-aryl 5-methylpyrrolidinones. Moreover, the safety and economic advantages of formic acid as a benign LOHC for this transformation were further confirmed by a comparison, with other H-sources, of the Ecoscale penalty points. The optimized extraction workup protocol allowed an E-factor reduction of 63% compared to a simple filtration for purification method. To further evidence the environmental improvement, Ecoscale was exploited, highlighting the benefits of our process in comparison to available literature protocols.
{"title":"Ecofriendly Reductive Amination of a Levulinic Acid Platform Molecule for the Synthesis of 5-Methyl-N-Aryl-Pyrrolidones Exploiting Formic Acid as an LOHC","authors":"Parvin Holakooei, Federica Valentini, Luigi Vaccaro","doi":"10.1021/acssuschemeng.4c08368","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08368","url":null,"abstract":"The unsustainable exploitation of fossil feedstocks for energy and chemical production has led, in the past few years, to the modern energy and environmental crisis, thus stimulating increased awareness in the definition of more sustainable alternatives. Among the transformations of biomass-derived levulinic acid, recognized as one of the top 10 platform molecules, the production of 5-methylpyrrolidinones is of great importance in diverse industrial fields. In this work, we defined a waste-minimized protocol for the production of <i>N</i>-aryl 5-methylpyrrolidinones, aiming both at the synergistic employment of a benign H-source and reaction media and at the optimization of the workup and purification step. The choice of formic acid as the hydrogen carrier and water as the solvent was beneficial for the replacement of gaseous hydrogen typically used in the synthesis of <i>N</i>-aryl 5-methylpyrrolidinones. Moreover, the safety and economic advantages of formic acid as a benign LOHC for this transformation were further confirmed by a comparison, with other H-sources, of the Ecoscale penalty points. The optimized extraction workup protocol allowed an E-factor reduction of 63% compared to a simple filtration for purification method. To further evidence the environmental improvement, Ecoscale was exploited, highlighting the benefits of our process in comparison to available literature protocols.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880252","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 : 2024-12-23DOI: 10.1021/acssuschemeng.4c09039
Fujie Wang, Qi Wang, Shuangqiao Yang
Epoxy resin (EP) is a widely used thermosetting resin. However, its cross-linked structure poses a big challenge for recycling into value-added products. This study advanced the recycling of acid anhydride-cured epoxy using solid-state shear milling (S3M) technology. Through this process, the C–C backbone and C–O cross-linking bonds in epoxy resins were destroyed, generating C═O and −OH reactive groups in the reactive epoxy resin powder (REP). When REP-20 (number of milling cycles) is incorporated as an active filler into the original curing system, the tensile strength of the epoxy resin increased from 34.2 to 51.6 MPa, and the flexural strength increased from 57.1 to 82.3 MPa, which were 50.1 and 44.1% enhancement, respectively, compared to REP-1. Futhermore, REP powder can serve as an active filler into epoxy resin with other curing agents, such as curing agent 593 and 4,4-Diaminodiphenylmethane (DDM). By employing REP powder to enhance surface roughness in hydrophobic coating, a contact angle increased 144.1°. Additionally, when REP was utilized in a filter column, it effectively separated water and oil with a separation efficiency of up to 99%. After 10 cycles of operation, the flux and filtration efficiency of the devices remained unchanged, demonstrating excellent stability and reusability. This study provided a new way to recycle thermosetting resins to produce value-added functional fillers for applications such as hydrophobic coatings and oil–water separation.
{"title":"Mechanochemical Recycling of Acid Anhydride-Cured Epoxy Resin for Functional Applications","authors":"Fujie Wang, Qi Wang, Shuangqiao Yang","doi":"10.1021/acssuschemeng.4c09039","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09039","url":null,"abstract":"Epoxy resin (EP) is a widely used thermosetting resin. However, its cross-linked structure poses a big challenge for recycling into value-added products. This study advanced the recycling of acid anhydride-cured epoxy using solid-state shear milling (S3M) technology. Through this process, the C–C backbone and C–O cross-linking bonds in epoxy resins were destroyed, generating C═O and −OH reactive groups in the reactive epoxy resin powder (REP). When REP-20 (number of milling cycles) is incorporated as an active filler into the original curing system, the tensile strength of the epoxy resin increased from 34.2 to 51.6 MPa, and the flexural strength increased from 57.1 to 82.3 MPa, which were 50.1 and 44.1% enhancement, respectively, compared to REP-1. Futhermore, REP powder can serve as an active filler into epoxy resin with other curing agents, such as curing agent 593 and 4,4-Diaminodiphenylmethane (DDM). By employing REP powder to enhance surface roughness in hydrophobic coating, a contact angle increased 144.1°. Additionally, when REP was utilized in a filter column, it effectively separated water and oil with a separation efficiency of up to 99%. After 10 cycles of operation, the flux and filtration efficiency of the devices remained unchanged, demonstrating excellent stability and reusability. This study provided a new way to recycle thermosetting resins to produce value-added functional fillers for applications such as hydrophobic coatings and oil–water separation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880251","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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