Xiaohua Wang, Hongfan Zhao, Yebin Zhou, Chunyu Yin, Wei He, Feng Feng, Fengli Wang, Chunshan Lu and Xiaonian Li
Biomass provides a promising source of carbon for obtaining environment-friendly carbon materials, but obtaining heteroatom-doped carbon materials (HDCMs) from biomass directly by a green method still remains challenging. This study successfully synthesized nitrogen and phosphorus co-doped porous carbon materials (Y-NPC) by the simple in situ pyrolysis of renewable yeast mixed with water from 800 to 950 °C. Various characterization methods show that nitrogen and phosphorus are doped into the carbon skeleton and mainly exist in the forms of graphite-N, pyridine-N, C–P, P–N, and P–O states. The catalyst Y-NPC-900 °C with a 3D hierarchical porous structure and high P–N content exhibited superior nitro hydrogenation performance and reaction stability using molecular hydrogen and hydrazine hydrate as hydrogen sources under mild conditions. Density functional theory (DFT) calculations and experiments attributed the exceptional catalytic performance to hydrogen activation and the good adsorption ability of substrates over N, P co-doped carbon (NPC). Therefore, this research proposes an eco-friendly and simple synthesis strategy for in situ N, P co-doping metal-free carbon catalysts derived from biomass, showing the significance of N, P co-doping and single N- or P-monodoping in the charge distribution of carbon materials.
生物质为获得环境友好型碳材料提供了一种前景广阔的碳源,但以绿色方法直接从生物质中获得掺杂杂原子的碳材料(HDCMs)仍然具有挑战性。本研究利用可再生酵母与水混合后在 800 至 950 °C 的温度下进行简单的原位热解,成功合成了氮磷共掺杂多孔碳材料(Y-NPC)。各种表征方法表明,氮和磷掺杂在碳骨架中,主要以石墨-N、吡啶-N、C-P、P-N 和 P-O 状态存在。催化剂 Y-NPC-900 °C 具有三维分层多孔结构和高 P-N 含量,在温和条件下以分子氢和水合肼为氢源,具有优异的硝基加氢性能和反应稳定性。密度泛函理论(DFT)计算和实验表明,N、P 共掺杂碳(NPC)的氢活化和对基质的良好吸附能力是其优异催化性能的主要原因。因此,本研究提出了一种环保、简单的生物质原位 N、P 共掺杂无金属碳催化剂合成策略,显示了 N、P 共掺杂和单一 N 或 P 单掺杂在碳材料电荷分布中的重要作用。
{"title":"Yeast-derived N, P co-doped porous green carbon materials as metal-free catalysts for selective hydrogenation of chloronitrobenzene†","authors":"Xiaohua Wang, Hongfan Zhao, Yebin Zhou, Chunyu Yin, Wei He, Feng Feng, Fengli Wang, Chunshan Lu and Xiaonian Li","doi":"10.1039/D4GC00993B","DOIUrl":"https://doi.org/10.1039/D4GC00993B","url":null,"abstract":"<p >Biomass provides a promising source of carbon for obtaining environment-friendly carbon materials, but obtaining heteroatom-doped carbon materials (HDCMs) from biomass directly by a green method still remains challenging. This study successfully synthesized nitrogen and phosphorus co-doped porous carbon materials (Y-NPC) by the simple <em>in situ</em> pyrolysis of renewable yeast mixed with water from 800 to 950 °C. Various characterization methods show that nitrogen and phosphorus are doped into the carbon skeleton and mainly exist in the forms of graphite-N, pyridine-N, C–P, P–N, and P–O states. The catalyst Y-NPC-900 °C with a 3D hierarchical porous structure and high P–N content exhibited superior nitro hydrogenation performance and reaction stability using molecular hydrogen and hydrazine hydrate as hydrogen sources under mild conditions. Density functional theory (DFT) calculations and experiments attributed the exceptional catalytic performance to hydrogen activation and the good adsorption ability of substrates over N, P co-doped carbon (NPC). Therefore, this research proposes an eco-friendly and simple synthesis strategy for <em>in situ</em> N, P co-doping metal-free carbon catalysts derived from biomass, showing the significance of N, P co-doping and single N- or P-monodoping in the charge distribution of carbon materials.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495446","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}
Lele Feng, Jin Guo, Jifeng Pang, Ming Yin, Yujia Zhao, Pengfei Wu, Mingyuan Zheng
Ethanol is the most abundant chemical widely used in the fuel additive sector. Currently, it is mainly produced by the fermentation process, but it suffers from low carbon balance and poor reaction efficiency issues. In the past few decades, several promising catalytic methods have been proposed for ethanol production, depending on the available energy resources, technology development, and government policy. Herein, the catalytic pathways for ethanol production from petroleum, coal, natural gas, CO2, and biomass in more sustainable ways are introduced. Specifically, the most crucial elementary steps in these catalytic pathways are reviewed and discussed, and key factors determining the feasibility of these catalytic reactions are listed, providing an all-around overview on the development of ethanol production in the near future. In the last section, an outlook was provided to highlight the challenges and opportunities for ethanol production and applications in more green and sustainable catalytic manners.
{"title":"Nonenzymatic ethanol production in sustainable ways","authors":"Lele Feng, Jin Guo, Jifeng Pang, Ming Yin, Yujia Zhao, Pengfei Wu, Mingyuan Zheng","doi":"10.1039/d4gc01584c","DOIUrl":"https://doi.org/10.1039/d4gc01584c","url":null,"abstract":"Ethanol is the most abundant chemical widely used in the fuel additive sector. Currently, it is mainly produced by the fermentation process, but it suffers from low carbon balance and poor reaction efficiency issues. In the past few decades, several promising catalytic methods have been proposed for ethanol production, depending on the available energy resources, technology development, and government policy. Herein, the catalytic pathways for ethanol production from petroleum, coal, natural gas, CO<small><sub>2</sub></small>, and biomass in more sustainable ways are introduced. Specifically, the most crucial elementary steps in these catalytic pathways are reviewed and discussed, and key factors determining the feasibility of these catalytic reactions are listed, providing an all-around overview on the development of ethanol production in the near future. In the last section, an outlook was provided to highlight the challenges and opportunities for ethanol production and applications in more green and sustainable catalytic manners.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141527186","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}
Noble-metal-free heterogeneous catalysts for deoxydehydration (DODH) using H2 as a reductant were developed. Among various transition metals examined as additives to modify the MoOx/TiO2 catalyst, Cu showed good conversion and selectivity in the transformation of 1,4-anhydroerythritol (1,4-AHERY) to 2,5-dihydrofuran (2,5-DHF). The performance of the MoOx–Cu/TiO2 catalysts was comparable to those modified with either Ag or Au instead of Cu. Upon the combination of two Mo precursors, i.e. (NH4)6Mo7O24 and Na2MoO4, the selectivity of the catalyst (MoOx–Cu–Na/TiO2) was further enhanced to achieve 81% yield of 2,5-DHF. This catalyst also exhibited broad substrate scope including cyclic and linear alkyl vicinal diols and tartaric ester. Furthermore, MoOx–Cu–Na/TiO2 was reusable at least three times after its calcination as regeneration. The reaction was almost zero-order with respect to the H2 pressure and 1,4-AHERY concentration, suggesting that the release of the alkene is the rate-determining step. The comprehensive characterization using STEM, XRD and XAFS provided insights into the surface structure of the catalyst, revealing that H2 is activated over Cu particles and subsequently transferred to Mo cluster species on the TiO2 surface via the spillover effect to proceed with the DODH reaction.
以 H2 为还原剂的脱氧脱水(DODH)无贵金属异相催化剂被开发出来。在作为添加剂改性 MoOx/TiO2 催化剂的各种过渡金属中,铜在将 1,4-anhydroerythritol (1,4-AHERY) 转化为 2,5-dihydrofuran (2,5-DHF) 的过程中表现出良好的转化率和选择性。MoOx-Cu/TiO2 催化剂的性能与用 Ag 或 Au 代替 Cu 改性的催化剂相当。将两种 Mo 前驱体(即 (NH4)6Mo7O24 和 Na2MoO4)结合使用后,催化剂(MoOx-Cu-Na/TiO2)的选择性进一步提高,2,5-DHF 的产率达到 81%。这种催化剂还具有广泛的底物范围,包括环状和线性烷基官能团二元醇和酒石酸酯。此外,MoOx-Cu-Na/TiO2 经煅烧再生后至少可重复使用三次。反应与 H2 压力和 1,4-AHERY 浓度几乎呈零阶关系,这表明烯的释放是决定反应速率的步骤。利用 STEM、XRD 和 XAFS 进行的综合表征深入揭示了催化剂的表面结构,揭示了 H2 在 Cu 颗粒上被激活,随后通过溢出效应转移到 TiO2 表面的 Mo 团簇物种上,从而进行 DODH 反应。
{"title":"Non-noble metal heterogeneous catalysts for hydrogen-driven deoxydehydration of vicinal diol compounds","authors":"Jianxing Gan, Yoshinao Nakagawa, Mizuho Yabushita, Keiichi Tomishige","doi":"10.1039/d4gc02006e","DOIUrl":"https://doi.org/10.1039/d4gc02006e","url":null,"abstract":"Noble-metal-free heterogeneous catalysts for deoxydehydration (DODH) using H<small><sub>2</sub></small> as a reductant were developed. Among various transition metals examined as additives to modify the MoO<small><sub><em>x</em></sub></small>/TiO<small><sub>2</sub></small> catalyst, Cu showed good conversion and selectivity in the transformation of 1,4-anhydroerythritol (1,4-AHERY) to 2,5-dihydrofuran (2,5-DHF). The performance of the MoO<small><sub><em>x</em></sub></small>–Cu/TiO<small><sub>2</sub></small> catalysts was comparable to those modified with either Ag or Au instead of Cu. Upon the combination of two Mo precursors, <em>i.e.</em> (NH<small><sub>4</sub></small>)<small><sub>6</sub></small>Mo<small><sub>7</sub></small>O<small><sub>24</sub></small> and Na<small><sub>2</sub></small>MoO<small><sub>4</sub></small>, the selectivity of the catalyst (MoO<small><sub><em>x</em></sub></small>–Cu–Na/TiO<small><sub>2</sub></small>) was further enhanced to achieve 81% yield of 2,5-DHF. This catalyst also exhibited broad substrate scope including cyclic and linear alkyl vicinal diols and tartaric ester. Furthermore, MoO<small><sub><em>x</em></sub></small>–Cu–Na/TiO<small><sub>2</sub></small> was reusable at least three times after its calcination as regeneration. The reaction was almost zero-order with respect to the H<small><sub>2</sub></small> pressure and 1,4-AHERY concentration, suggesting that the release of the alkene is the rate-determining step. The comprehensive characterization using STEM, XRD and XAFS provided insights into the surface structure of the catalyst, revealing that H<small><sub>2</sub></small> is activated over Cu particles and subsequently transferred to Mo cluster species on the TiO<small><sub>2</sub></small> surface <em>via</em> the spillover effect to proceed with the DODH reaction.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141527187","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}
Sohaib Hameed, Wengang Liu, Zhounan Yu, Jifeng Pang, Wenhao Luo and Aiqin Wang
2,5-Furandicarboxylic acid (FDCA) is one of the most promising biodegradable substitutes for fossil-derived terephthalic acid (PTA) and adipic acid. The production of FDCA from biomass-derived 5-hydroxymethylfurfural (HMF) is significant and has attracted great attention. However, the major challenge lies in the development of a non-precious metal-based catalyst system without employing a homogeneous base. Herein, we successfully prepared an atomically dispersed Fe–N–C/γ-Al2O3 catalyst, which affords superior catalytic performance in terms of activity and stability with a FDCA yield of 99.8% and reusability of five recycle times in the catalytic oxidation of HMF to FDCA under base-free mild conditions. Based on controlled experiments and complementary characterization studies, we found that the atomically dispersed medium-spin Fe–N5 active sites together with the surface acidic/basic sites of alumina synergistically enhanced the catalytic activity and selectivity towards FDCA under base-free conditions. Our process eliminates the employment of expensive oxidants and corrosive bases, leading to economic and green biomass transformations.
{"title":"Base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over a Fe single-atom catalyst†","authors":"Sohaib Hameed, Wengang Liu, Zhounan Yu, Jifeng Pang, Wenhao Luo and Aiqin Wang","doi":"10.1039/D4GC01777C","DOIUrl":"https://doi.org/10.1039/D4GC01777C","url":null,"abstract":"<p >2,5-Furandicarboxylic acid (FDCA) is one of the most promising biodegradable substitutes for fossil-derived terephthalic acid (PTA) and adipic acid. The production of FDCA from biomass-derived 5-hydroxymethylfurfural (HMF) is significant and has attracted great attention. However, the major challenge lies in the development of a non-precious metal-based catalyst system without employing a homogeneous base. Herein, we successfully prepared an atomically dispersed Fe–N–C/γ-Al<small><sub>2</sub></small>O<small><sub>3</sub></small> catalyst, which affords superior catalytic performance in terms of activity and stability with a FDCA yield of 99.8% and reusability of five recycle times in the catalytic oxidation of HMF to FDCA under base-free mild conditions. Based on controlled experiments and complementary characterization studies, we found that the atomically dispersed medium-spin Fe–N<small><sub>5</sub></small> active sites together with the surface acidic/basic sites of alumina synergistically enhanced the catalytic activity and selectivity towards FDCA under base-free conditions. Our process eliminates the employment of expensive oxidants and corrosive bases, leading to economic and green biomass transformations.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495469","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}
Yifan Han, Jiachangli Shang, Shuai Yin, Rong Cao, Jing Zhang, Wei Jiang, Guigao Liu
Ammonia (NH3) is a pivotal component for the majority of fertilizers, chemicals, and pharmaceuticals. Its conventional production through the Haber–Bosch process is highly energy-intensive and significantly contributes to CO2 emissions, thereby exacerbating global warming. In parallel, the overuse of agricultural fertilizers and the inadequate industrial wastewater management cause the heavy nitrate (NO3−) pollution which poses huge environmental and health hazards to human beings. In an effort to address these challenges, scientists have been exploring more sustainable methods of ammonia synthesis and strategies to mitigate nitrate pollution. Among these, the electrocatalytic reduction of nitrates to ammonia/ammonium (NO3RR) presents a promising solution. This innovative approach not only reduces the environmental footprint of ammonia production by operating under ambient conditions but also contributes to the purification of water bodies by lowering nitrate levels. This review intricately explores the complexities involved in the electrocatalytic reduction of nitrates to ammonia, shedding light on the nuanced mechanisms underlying the process and elucidating the importance of symmetry-breaking structures. It particularly underscores the pivotal role played by various symmetry-breaking structures in catalysts, which serve to disrupt and invigorate the reaction environment, thus enhancing the efficiency of the electrocatalytic process. In culmination, we offer a comprehensive summary of the advancements in the development of catalysts featuring symmetry-breaking structures, providing insights and forward-looking recommendations for the future engineering of broadly applicable symmetry-breaking structure catalysts.
{"title":"Symmetry-breaking structure electrocatalysts for nitrate reduction to ammonia","authors":"Yifan Han, Jiachangli Shang, Shuai Yin, Rong Cao, Jing Zhang, Wei Jiang, Guigao Liu","doi":"10.1039/d4gc02069c","DOIUrl":"https://doi.org/10.1039/d4gc02069c","url":null,"abstract":"Ammonia (NH<small><sub>3</sub></small>) is a pivotal component for the majority of fertilizers, chemicals, and pharmaceuticals. Its conventional production through the Haber–Bosch process is highly energy-intensive and significantly contributes to CO<small><sub>2</sub></small> emissions, thereby exacerbating global warming. In parallel, the overuse of agricultural fertilizers and the inadequate industrial wastewater management cause the heavy nitrate (NO<small><sub>3</sub></small><small><sup>−</sup></small>) pollution which poses huge environmental and health hazards to human beings. In an effort to address these challenges, scientists have been exploring more sustainable methods of ammonia synthesis and strategies to mitigate nitrate pollution. Among these, the electrocatalytic reduction of nitrates to ammonia/ammonium (NO<small><sub>3</sub></small>RR) presents a promising solution. This innovative approach not only reduces the environmental footprint of ammonia production by operating under ambient conditions but also contributes to the purification of water bodies by lowering nitrate levels. This review intricately explores the complexities involved in the electrocatalytic reduction of nitrates to ammonia, shedding light on the nuanced mechanisms underlying the process and elucidating the importance of symmetry-breaking structures. It particularly underscores the pivotal role played by various symmetry-breaking structures in catalysts, which serve to disrupt and invigorate the reaction environment, thus enhancing the efficiency of the electrocatalytic process. In culmination, we offer a comprehensive summary of the advancements in the development of catalysts featuring symmetry-breaking structures, providing insights and forward-looking recommendations for the future engineering of broadly applicable symmetry-breaking structure catalysts.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141527190","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 demand for fermentation-based chemicals is expected to grow in the coming years because of the increasing emphasis on using bio-based chemicals over petrochemicals. Growing crude oil prices and rising concerns about carbon discharge are the main reasons pushing the shift toward bio-based chemicals. 2,3-Pentanedione is one such high-value fine chemical that is currently produced in smaller quantities through a multi-stage chemical synthesis or extracted from milk waste. Here we report a green route to produce 2,3–pentanedione directly from vapour-phase condensation of crude lactic acid over polymorphic ZrO2. The catalyst exhibits high selectivity, activity and stability for the direct condensation of raw lactic acid to 2,3-pentanedione and achieved 99.7% LA conversion and 95.5% selectivity at 325 °C.
由于人们越来越重视使用生物基化学品而非石化产品,预计未来几年对发酵基化学品的需求将有所增长。原油价格的不断上涨和人们对碳排放的日益关注是推动向生物基化学品转变的主要原因。2,3-戊二酮就是这样一种高价值的精细化学品,目前通过多级化学合成或从牛奶废料中提取的方法只能少量生产。在这里,我们报告了一条在多晶态 ZrO2 上直接从粗乳酸气相缩合生产 2,3-戊二酮的绿色路线。该催化剂在将原料乳酸直接缩合为 2,3-戊二酮的过程中表现出高选择性、高活性和高稳定性,在 325 °C 的温度下实现了 99.7% 的 LA 转化率和 95.5% 的选择性。
{"title":"Highly efficient production of 2,3-pentanedione from condensation of bio-derived lactic acid over polymorphic ZrO2","authors":"Neha Dhiman, B. Moses Abraham, Deepti Agrawal, Sudhakara Reddy Yenumala, Jyoti Porwal, Bipul Sarkar","doi":"10.1039/d4gc02097a","DOIUrl":"https://doi.org/10.1039/d4gc02097a","url":null,"abstract":"The demand for fermentation-based chemicals is expected to grow in the coming years because of the increasing emphasis on using bio-based chemicals over petrochemicals. Growing crude oil prices and rising concerns about carbon discharge are the main reasons pushing the shift toward bio-based chemicals. 2,3-Pentanedione is one such high-value fine chemical that is currently produced in smaller quantities through a multi-stage chemical synthesis or extracted from milk waste. Here we report a green route to produce 2,3–pentanedione directly from vapour-phase condensation of crude lactic acid over polymorphic ZrO<small><sub>2</sub></small>. The catalyst exhibits high selectivity, activity and stability for the direct condensation of raw lactic acid to 2,3-pentanedione and achieved 99.7% LA conversion and 95.5% selectivity at 325 °C.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141527188","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}
Ji-Wei Sang, Hong Chen, Yu Zhang, Jinxin Wang and Wei-Dong Zhang
N-Nitrosamines represent a class of bifunctional nitrogen-radical precursors, but their application potential remains largely unexplored. This study reports the highly atom-economical production of diverse α-oximino sulfonamides via direct photo-mediated radical relay oximinosulfonamidation of activated or unactivated alkenes with N-nitrosamines triggered by organic sulfide. N-Nitrosamines worked as bifunctional reagents in this transformation, simultaneously generating aminyl radicals and NO radicals. The organic sulfide was designed to act as a radical decaging agent as well as a source of sulfonyl. Its strong radical capturing ability and affinity for alkenes enable the rapid capturing of the aminyl radicals, thereby inhibiting the rapid recombination of radical pairs in the solvent cage. The synthesized oxime units could also be easily converted into other functional groups, leading to selective downstream transformations. The mild photodegradation reaction of harmful N-nitrosoamines showed high functional group tolerance and compatibility, facilitating the late-stage functionalization of natural products and drug molecules, expanding the biologically relevant chemical space.
亚硝胺是一类双功能氮-自由基前体,但其应用潜力在很大程度上仍未得到开发。本研究报告了在有机硫化物的触发下,通过 N-亚硝胺对活化或未活化烯烃的直接光介导自由基中继氧化亚氨基磺酰胺化反应,以高度原子经济的方式生产出多种α-氧亚氨基磺酰胺。在这一转化过程中,N-亚硝胺作为双功能试剂起作用,同时产生氨基自由基和 NO 自由基。有机硫化物被设计为自由基衰减剂和磺酰的来源。其强大的自由基捕获能力和对烯烃的亲和力可快速捕获氨自由基,从而抑制自由基对在溶剂笼中的快速重组。合成的肟单元也很容易转化为其他官能团,从而实现选择性下游转化。有害 N-亚硝基胺的温和光降解反应显示出较高的官能团耐受性和兼容性,有利于天然产物和药物分子的后期官能化,拓展了生物相关化学空间。
{"title":"Photo-mediated radical relay oximinosulfonamidation of alkenes with N-nitrosamines triggered by DABSO†","authors":"Ji-Wei Sang, Hong Chen, Yu Zhang, Jinxin Wang and Wei-Dong Zhang","doi":"10.1039/D4GC01976H","DOIUrl":"https://doi.org/10.1039/D4GC01976H","url":null,"abstract":"<p > <em>N</em>-Nitrosamines represent a class of bifunctional nitrogen-radical precursors, but their application potential remains largely unexplored. This study reports the highly atom-economical production of diverse α-oximino sulfonamides <em>via</em> direct photo-mediated radical relay oximinosulfonamidation of activated or unactivated alkenes with <em>N</em>-nitrosamines triggered by organic sulfide. <em>N</em>-Nitrosamines worked as bifunctional reagents in this transformation, simultaneously generating aminyl radicals and NO radicals. The organic sulfide was designed to act as a radical decaging agent as well as a source of sulfonyl. Its strong radical capturing ability and affinity for alkenes enable the rapid capturing of the aminyl radicals, thereby inhibiting the rapid recombination of radical pairs in the solvent cage. The synthesized oxime units could also be easily converted into other functional groups, leading to selective downstream transformations. The mild photodegradation reaction of harmful <em>N</em>-nitrosoamines showed high functional group tolerance and compatibility, facilitating the late-stage functionalization of natural products and drug molecules, expanding the biologically relevant chemical space.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495453","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}
Sebastian Stahl, Niklas Wessel, Andreas J. Vorholt and Walter Leitner
A simple and recyclable homogeneous catalytic system for the hydrogenation of carbon monoxide to methanol was established. The reaction is catalyzed by a molecular manganese complex using a high-boiling alcohol as the solvent for catalyst immobilization. The CO hydrogenation is assisted by the product itself and the solvent through the formation of a methyl or dodecyl formate ester intermediate mediated by catalytic amounts of NaOMe as the base. This allows the catalytic formation of methanol in alcohols combined with facile product separation and catalyst recycling via distillation. Initial turnover frequencies (TOF) of 2250 h−1 were reached under optimized conditions in 1-dodecanol/methanol as the reaction medium (T = 160 °C, p(H2/CO) = 80/10 bar). The performance was stabilized in batch-wise recycling over 6 runs achieving a total turnover number (TTON) of >12 000 corresponding to an enhancement of more than five times compared to single batch operation under identical conditions. Minimal leaching of the components of the organometallic catalyst was observed during distillative product separation and catalyst activity could be fully restored by re-addition of the base NaOMe.
{"title":"Liquid-phase hydrogenation of carbon monoxide to methanol using a recyclable manganese-based catalytic system†","authors":"Sebastian Stahl, Niklas Wessel, Andreas J. Vorholt and Walter Leitner","doi":"10.1039/D4GC01050G","DOIUrl":"https://doi.org/10.1039/D4GC01050G","url":null,"abstract":"<p >A simple and recyclable homogeneous catalytic system for the hydrogenation of carbon monoxide to methanol was established. The reaction is catalyzed by a molecular manganese complex using a high-boiling alcohol as the solvent for catalyst immobilization. The CO hydrogenation is assisted by the product itself and the solvent through the formation of a methyl or dodecyl formate ester intermediate mediated by catalytic amounts of NaOMe as the base. This allows the catalytic formation of methanol in alcohols combined with facile product separation and catalyst recycling <em>via</em> distillation. Initial turnover frequencies (TOF) of 2250 h<small><sup>−1</sup></small> were reached under optimized conditions in 1-dodecanol/methanol as the reaction medium (<em>T</em> = 160 °C, <em>p</em>(H<small><sub>2</sub></small>/CO) = 80/10 bar). The performance was stabilized in batch-wise recycling over 6 runs achieving a total turnover number (TTON) of >12 000 corresponding to an enhancement of more than five times compared to single batch operation under identical conditions. Minimal leaching of the components of the organometallic catalyst was observed during distillative product separation and catalyst activity could be fully restored by re-addition of the base NaOMe.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc01050g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Over the past few years, the proliferation of lithium-ion batteries (LIBs) as pivotal energy storage solutions has surged dramatically. However, this widespread adoption has come with a significant downside: the accumulation of substantial quantities of discarded LIBs. From the perspective of green production and industrial development, the problem of recycling spent LIBs urgently needs to be addressed. Based on the physicochemical properties of ionic liquids (ILs) and deep eutectic solvents (DESs), as well as their potential in LIB recycling, this paper proposes the concept of the Ionic Liquid System, including ILs and DESs. The aim is to systematically outline the application of the Ionic Liquid System in the LIB recycling industry. Ionic Liquid System reagents are considered environmentally friendly green solvents due to their biodegradability. Here, we discuss laboratory research on the recovery of spent LIBs using similar system solvents based on studies reported over the past decade and categorize recent laboratory work, while evaluating the advantages and disadvantages of the application of the Ionic Liquid System. This article explicitly provides an effective reference for recycling spent LIBs through the Ionic Liquid System and prospects for future work on recycling spent lithium batteries.
在过去几年中,锂离子电池(LIB)作为重要的能源存储解决方案得到了迅猛发展。然而,锂离子电池的广泛应用也带来了一个严重的弊端:大量废弃锂离子电池的积累。从绿色生产和工业发展的角度来看,废弃锂电池的回收问题亟待解决。基于离子液体(ILs)和深共晶溶剂(DESs)的物理化学特性及其在 LIB 回收利用中的潜力,本文提出了离子液体系统(包括 ILs 和 DESs)的概念。目的是系统地概述离子液体系统在锂离子电池回收行业中的应用。离子液体系统试剂具有生物降解性,因此被认为是对环境友好的绿色溶剂。在此,我们根据过去十年的研究报告,讨论了使用类似系统溶剂回收废 LIB 的实验室研究,并对近期的实验室工作进行了分类,同时评估了离子液体系统应用的优缺点。本文明确提出了通过离子液体系统回收废锂电池的有效参考方法,并对未来回收废锂电池的工作进行了展望。
{"title":"Review of the application of ionic liquid systems in achieving green and sustainable recycling of spent lithium-ion batteries","authors":"Huiying Shi, Yi Luo, Chengzhe Yin, Leming Ou","doi":"10.1039/d4gc01207k","DOIUrl":"https://doi.org/10.1039/d4gc01207k","url":null,"abstract":"Over the past few years, the proliferation of lithium-ion batteries (LIBs) as pivotal energy storage solutions has surged dramatically. However, this widespread adoption has come with a significant downside: the accumulation of substantial quantities of discarded LIBs. From the perspective of green production and industrial development, the problem of recycling spent LIBs urgently needs to be addressed. Based on the physicochemical properties of ionic liquids (ILs) and deep eutectic solvents (DESs), as well as their potential in LIB recycling, this paper proposes the concept of the Ionic Liquid System, including ILs and DESs. The aim is to systematically outline the application of the Ionic Liquid System in the LIB recycling industry. Ionic Liquid System reagents are considered environmentally friendly green solvents due to their biodegradability. Here, we discuss laboratory research on the recovery of spent LIBs using similar system solvents based on studies reported over the past decade and categorize recent laboratory work, while evaluating the advantages and disadvantages of the application of the Ionic Liquid System. This article explicitly provides an effective reference for recycling spent LIBs through the Ionic Liquid System and prospects for future work on recycling spent lithium batteries.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141527189","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}
Xiaohui Yao, Changyan Zhu, Jie Zhou, Kunhao Zhang, Chunyi Sun, Man Dong, Guogang Shan, Zhuo Wu, Min Zhang, Xinlong Wang and Zhongmin Su
The development of electrocatalysts that convert CO2 and N2 in flue gas to directly usable urea does not only explore the hidden value of exhaust gas but also alleviates the global environmental issues caused by excessive CO2 emissions; yet, related research studies are still in their infancy. Herein, multi-porous Cu–W18O49@ZIF-8, composed of ultra-small nanosized ZIF-8 on Cu-doped W18O49 nanowires, was fabricated as a urea-generation electrocatalyst in flue gas. It exhibits an appealing Faraday efficiency of urea up to 16.1% at −0.9 V (vs. RHE) and an outstanding yield of 1.33 mmol g−1 h−1 at −1.0 V (vs. RHE) under the flue gas atmosphere. The catalytic performance was maintained for a wide range of N2 : CO2 ratios. Theoretical calculations indicate that the doped copper regulates the electron density around the adjacent W–W, which facilitates N2 adsorption, partly suppresses the HER side reaction, and decreases the ΔG of the following multi-step hydrogenation after *CO insertion until urea production.
{"title":"Boosting urea synthesis in simulated flue gas electroreduction by adjusting W–W electronic properties†","authors":"Xiaohui Yao, Changyan Zhu, Jie Zhou, Kunhao Zhang, Chunyi Sun, Man Dong, Guogang Shan, Zhuo Wu, Min Zhang, Xinlong Wang and Zhongmin Su","doi":"10.1039/D4GC02536A","DOIUrl":"https://doi.org/10.1039/D4GC02536A","url":null,"abstract":"<p >The development of electrocatalysts that convert CO<small><sub>2</sub></small> and N<small><sub>2</sub></small> in flue gas to directly usable urea does not only explore the hidden value of exhaust gas but also alleviates the global environmental issues caused by excessive CO<small><sub>2</sub></small> emissions; yet, related research studies are still in their infancy. Herein, multi-porous Cu–W<small><sub>18</sub></small>O<small><sub>49</sub></small>@ZIF-8, composed of ultra-small nanosized ZIF-8 on Cu-doped W<small><sub>18</sub></small>O<small><sub>49</sub></small> nanowires, was fabricated as a urea-generation electrocatalyst in flue gas. It exhibits an appealing Faraday efficiency of urea up to 16.1% at −0.9 V (<em>vs.</em> RHE) and an outstanding yield of 1.33 mmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> at −1.0 V (<em>vs.</em> RHE) under the flue gas atmosphere. The catalytic performance was maintained for a wide range of N<small><sub>2</sub></small> : CO<small><sub>2</sub></small> ratios. Theoretical calculations indicate that the doped copper regulates the electron density around the adjacent W–W, which facilitates N<small><sub>2</sub></small> adsorption, partly suppresses the HER side reaction, and decreases the Δ<em>G</em> of the following multi-step hydrogenation after *CO insertion until urea production.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141495436","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}