Green Chemistry最新文献

{"title":"Harnessing borane-potassium cooperativity for sulfurated ring-opening copolymerisation†","authors":"Bhargav R. Manjunatha ,&nbsp;Kailey Sun Marcus ,&nbsp;Rosa M. Gomila ,&nbsp;Antonio Frontera ,&nbsp;Alex J. Plajer","doi":"10.1039/d4gc05665e","DOIUrl":"10.1039/d4gc05665e","url":null,"abstract":"<div><div>Sulfur-containing polymers, such as thioesters and thiocarbonates, can exhibit improved thermal properties and degradability compared to their all-oxygen analogues, yet their synthesis remains challenging. In this respect, ring-opening copolymerization (ROCOP) offers access to sulfur-containing polymers; however, the catalysts used for this process often rely on toxic, expensive or synthetically complex components. Here, we demonstrate that combining commercial borane Lewis acids with easily accessible potassium acetate crown ether complexes highly selectively mediates the ring-opening copolymerization of oxetanes with a wide range of sulfur-containing monomers. Mechanistic investigations clearly indicate a cooperative mode of action between boron and potassium, yielding high-melting, semicrystalline materials that exhibit improved thermal stability compared to those generated <em>via</em> chromium catalysis. Our study establishes new concepts in cooperative catalysis to produce sustainable materials that are otherwise difficult to access.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3494-3502"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc05665e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676101","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}

{"title":"Boosting the efficient alkaline seawater oxygen evolution reaction of iron oxide hydroxide via plasma-induced oxygen defect engineering†","authors":"Xiaoqian Du ,&nbsp;Junjun Zhang ,&nbsp;Xuanyu Zhou ,&nbsp;Mengyuan Zhang ,&nbsp;Nailiang Wang ,&nbsp;Xiu Lin ,&nbsp;Pengfei Zhang ,&nbsp;Zhenghong Luo","doi":"10.1039/d5gc00368g","DOIUrl":"10.1039/d5gc00368g","url":null,"abstract":"<div><div>Obtaining hydrogen through direct decomposition of seawater is highly significant for alleviating the increasing shortage of freshwater resources. Nonetheless, a major obstacle to the oxidation of saltwater is the severe corrosion of anodes by Cl⁻ ions. In this work, a wet chemical technique and argon plasma treatment were used to obtain defect-rich FeOOH/SS electrodes for the OER in a basic electrolyte and simulated seawater. The findings from EPR and XAFS showed that a significant number of oxygen vacancies were generated through the plasma treatment. These vacancies promoted the activation of lattice oxygen during the oxidation of water. The findings showed that plentiful oxygen vacancies in P-FeOOH/SS provided a substantial number of active sites and facilitated efficient electron transfer, both of which greatly increased OER activity. Notably, when the electrolyte was simulated seawater (1.0 M KOH and 0.5 M NaCl), the overpotential reached 278 mV at 10 mA cm⁻². Under these conditions, the Tafel slope was measured at 32.66 mV dec⁻¹. Furthermore, the stability was maintained at 50 mA cm⁻² for more than 100 hours. Theoretical calculations showed that the high catalytic activity was primarily due to the positive effects of oxygen defects on the electron density and the d-band center of the active site. This research presented a straightforward approach for the development of efficacious defect-rich electrodes for alkaline seawater electrolysis.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3515-3523"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676176","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}

{"title":"Tailored mechanical properties of soybean oil-based non-isocyanate polyurethanes by copolymer integration†","authors":"Byeongju Jeon ,&nbsp;Kyoungmun Lee ,&nbsp;Jihoon Shin ,&nbsp;Siyoung Q. Choi","doi":"10.1039/d5gc00058k","DOIUrl":"10.1039/d5gc00058k","url":null,"abstract":"<div><div>Stiff thermoset polyurethane (PU) plays a crucial role in high-performance applications, particularly in industries requiring exceptional mechanical integrity, chemical resistance, and thermal stability. To reduce the environmental impact of PU production, (i) soybean oil has emerged as a renewable and abundant alternative to petroleum-based feedstocks, offering biodegradability and a reduced carbon footprint, while (ii) non-isocyanate polyurethane (NIPU) provides a greener approach by eliminating hazardous isocyanate compounds and avoiding isocyanate-functionalized chemicals. However, the development of soybean oil-based NIPU faces challenges in achieving the desired stiffness and resistance against fracture due to the large molecular size and inconsistent structure of soybean oil, which result in low crosslinking density and a lack of short-range ordering. To address the limitations of soybean oil-based NIPU, we developed a method that restricts polymer network relaxation by incorporating short-range ordered polymer segments using a copolymer with ethyl methacrylate (EMA) segments. Surpassing the highest mechanical properties reported for soybean oil-based NIPU to date, co-NIPU-<em>x</em> derived from copolymers with higher EMA content exhibits improved mechanical properties, demonstrating a four-fold increase in Young's modulus and a two-fold increase in tensile stress. The adjustable poly(2-aminoethylmethacrylate-<em>ran</em>-ethylmethacryate) (poly(AEMA-<em>ran</em>-EMA)) composition ratio allows for a wide range of mechanical properties, with Young's modulus ranging from 60 to 1030 MPa and tensile stress from 2.1 to 25 MPa. Furthermore, these NIPU samples exhibited enhanced adhesion properties with lap shear strength exceeding 7 MPa, significantly higher than those of traditional formulations. The thermal stability was improved with the NIPU samples resisting structural degradation, and chemical resistance was confirmed by sufficient swelling ratios in both hydrophilic and hydrophobic solvents, underscoring their suitability for a broader range of industrial applications.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3559-3572"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d5gc00058k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676167","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}

{"title":"Realizing CO2 emission reduction in lime and soda ash manufacturing through anion exchange†","authors":"Aniruddha Baral ,&nbsp;Jose-Luis Galvez-Martos ,&nbsp;Theodore Hanein","doi":"10.1039/d4gc05568c","DOIUrl":"10.1039/d4gc05568c","url":null,"abstract":"<div><div>Lime (CaO) and soda ash (Na₂CO₃) are two foundational chemicals for modern civilization, and the CO₂ emissions from their production processes are challenging to reduce. Furthermore, decarbonization of the lime industry could also reduce the CO₂ emissions associated with cement production, for which lime is the key precursor. In this paper, we show that an anion exchange process to co-produce CaO and Na₂CO₃ from CaCO₃ and NaOH can reduce the carbon footprint of both chemicals through industrial symbiosis. Heating energy and NaOH production are the major contributing factors towards the cost and CO₂ emissions of this process, which can supply the global annual soda ash demand (∼65 Mt) and co-produce ∼50 Mt of lime in an economically sustainable manner (16% gross margin) while immediately reducing global CO₂ emission by 37 Mt compared to current production methods. Using electrified industrial heat sources and heat pumps to reuse heating energy would further reduce the cost and CO₂ emissions of the anion exchange process.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3431-3442"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc05568c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676180","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}

{"title":"Dual-function thiourea for photochemical recovery of precious metals in an Fe(iii)-oxalate based system†","authors":"Guangbing Liang ,&nbsp;Hui Wang ,&nbsp;Zhenping Qu","doi":"10.1039/d4gc06172a","DOIUrl":"10.1039/d4gc06172a","url":null,"abstract":"<div><div>It is urgent to bring out an eco-friendly and high-efficiency strategy for efficient hydrometallurgical recovery of precious metals (PMs) to avoid the use of highly corrosive and strongly poisonous solvents. In this work, it has been found that PMs of Au, Pt, and Pd can be almost completely recovered at room temperature (RT) <em>via</em> a simulated-sunlight (SSL) irradiation route. Maximum recovery amounts of Au, Pt, and Pd are 6.0, 1.2, and 5.0 mg L⁻¹ in an appropriate FOC-T system including 0.02/0.05/0.05 mol L⁻¹ Fe(<span>iii</span>)-oxalate complexes (FOC) and 40/60/60 g L⁻¹ thiourea, respectively. Thiourea plays a dual-function role in increasing the amount and prolonging the lifetime of reactive oxygen radicals in the photo-dissolution system by the generation of sulfate radicals from thiourea oxidation during the photodegradation of FOC, and constructing the coordination of PMs during the photochemical dissolution process using thiocarbonyl groups of thiourea as the active coordination sites. As a result, the FOC-T system exhibits a superiority in the recovery performance of PMs with a low FOC concentration compared with the FOC-Cl system (∼100% <em>versus</em> &lt;20%), and the obtained PM-containing lixivium can act well as a precursor similar to commercial H₂PtCl₆, HAuCl₄, and (NH₄)₂PdCl₄ for catalyst preparation. In brief, this work provides a new approach for the photochemical recovery of PMs in a green FOC-T dissolution system and enriches the development of novel recovery methods for PMs.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3503-3514"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676183","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}

{"title":"Upgrading of waste polyolefins with non-noble metal catalysts","authors":"Jiahui Zhan ,&nbsp;Ruihong Dai ,&nbsp;Rongfei Cong ,&nbsp;Yitong Dan ,&nbsp;Hu Luo ,&nbsp;Haozhi Zhou ,&nbsp;Lin Xia ,&nbsp;Shicheng Zhang ,&nbsp;Hui Wang","doi":"10.1039/d4gc06105e","DOIUrl":"10.1039/d4gc06105e","url":null,"abstract":"<div><div>The rapid growth of waste polyolefin plastics poses a great threat to the environment and human health; hence there is an urgent requirement of efficient and environment-friendly upgrading methods. Aiming to utilize these hazardous substances and reduce energy consumption in a green way, most of the current studies use noble metal catalysts for the conversion of plastic waste, while non-noble metal catalysts have gradually attracted attention in the upgrading of waste polyolefins due to their abundant reserves, low cost, and potential to offer more sustainable alternatives. This paper provides a comprehensive review of Ni and Co-based and other catalysts in the hydrocracking, hydrogenolysis and tandem catalysis of polyolefins in recent years. It highlights the significance of the catalyst composition and support structure, which are key factors in determining the efficiency and selectivity of the conversion processes. The structure–activity relationships of these catalysts are also discussed to reveal how active site and structure design can influence the yield of desirable products while minimizing by-product formation and environmental impact. In addition, the challenges and prospects of non-noble metal catalysts in the selective upgrading of waste polyolefins in a circular economy are described to provide a theoretical foundation for the design and development of more efficient and stable catalysts, while inspiring further research in the green upgrading of waste polyolefins.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3398-3412"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676179","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}

{"title":"Electrophotochemical ligand-to-metal charge transfer catalysis: an emerging platform for sustainable synthesis","authors":"Haonan Zhang ,&nbsp;Dengchao Wei ,&nbsp;Kun Xu ,&nbsp;Chengchu Zeng","doi":"10.1039/d5gc00186b","DOIUrl":"10.1039/d5gc00186b","url":null,"abstract":"<div><div>Electrophotochemical ligand-to-metal charge transfer (LMCT) catalysis has contributed to advancing sustainable radical chemistry by exploiting both visible light and electricity as clean energy inputs. Moreover, electrophotochemical LMCT catalysis is not only beneficial for selective activation of metal-bound ligands even in the presence of more electron-rich moieties, but also exhibits high functional group compatibility due to the low operating potentials resulting from the inherent inner-sphere reactivity mode. Here we highlight the advancements in the field of electrophotochemical LMCT catalysis, with an emphasis on the substrate scope, reaction limitations as well as mechanistic insights. At the end of this review, we provide our views on current challenges and future potential opportunities in this emerging field.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3413-3430"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676182","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}

{"title":"Engineering budding yeast for the de novo synthesis of valuable flavanone derivatives†","authors":"Si-Yu Zhu ,&nbsp;Na Li ,&nbsp;Zhi-Hua Liu ,&nbsp;Ying-Jin Yuan ,&nbsp;Bing-Zhi Li","doi":"10.1039/d4gc05241b","DOIUrl":"10.1039/d4gc05241b","url":null,"abstract":"<div><div>Flavonoids, such as homoeriodictyol derivatives, hold significant value in nutraceuticals, foods, and pharmaceuticals. Microbial synthesis of these products has emerged as a powerful approach due to its sustainability and environmental friendliness. However, constructing microbial cell factories of homoeriodictyol derivatives is often challenged by the lack of a biosynthesis pathway and the poor performance of endogenous metabolic networks. Here, an efficient <em>Saccharomyces cerevisiae</em> cell factory was designed and metabolically engineered for the <em>de novo</em> biosynthesis of homoeriodictyol 7-<em>O</em>-glucoside. Relieving the feedback inhibition and overexpressing the key enzymes successfully achieved the biosynthesis of homoeriodictyol with a titer of 174.0 mg L⁻¹. Enzyme screening strategies explored missing glycosyltransferases and unveiled the homoeriodictyol 7-<em>O</em>-glucoside synthesis pathway for the first time. Blocking the glycoside hydrolysis pathway improved the titer of homoeriodictyol 7-<em>O</em>-glucoside by a substantial 7.2-fold. Metabolically regulating NADPH regeneration reduced the intermediate accumulation by 91.3%, while strengthening uridine diphosphate-glucose and substrate supply further boosted the homoeriodictyol 7-<em>O</em>-glucoside production. Altogether, these advancements led to a record homoeriodictyol 7-<em>O</em>-glucoside titer of 600.2 mg L⁻¹ and a yield of 12.2 mg g⁻¹ glucose. Overall, the versatile <em>S. cerevisiae</em> cell factory shows the potential to synthesize homoeriodictyol 7-<em>O</em>-glucoside, contributing to the green and sustainable production of natural products.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3477-3493"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676178","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}

{"title":"Recent advances in heterogeneous catalysts for biocrude hydrodeoxygenation","authors":"Penghui Yan ,&nbsp;Eric M. Kennedy ,&nbsp;Hesamoddin Rabiee ,&nbsp;Yilun Weng ,&nbsp;Hong Peng ,&nbsp;Beibei Ma ,&nbsp;Zhonghua Zhu ,&nbsp;Michael Stockenhuber","doi":"10.1039/d4gc05059b","DOIUrl":"10.1039/d4gc05059b","url":null,"abstract":"<div><div>Hydrodeoxygenation (HDO) of biocrude into chemicals and transportation fuels represents a promising avenue for the sustainable utilization of biomass-derived biocrude oil, obtained through pyrolysis or liquefaction. Catalysts play a pivotal role in this process, providing active metal sites for hydrogenation and hydrogenolysis, alongside acid sites for ring-opening, cracking, and C–O bond cleavage. Despite its potential, previous studies have often reported low HDO rates, leading to rapid catalyst deactivation and the formation of undesirable byproducts. Thus, the careful selection of catalysts that achieve an optimal balance between metal and acid functionality is critical. This review systematically examines the properties of biocrude produced by various techniques and the catalysts used in HDO of biocrude and its model compounds. Particular attention is given to the roles of sulfided metals, noble metals, non-noble metals as catalysts as well as various supports in HDO reactions. The influence of catalyst characteristics, including metal particle size, acid type and strength, and support structure, on HDO activity and product distribution is thoroughly analyzed. Additionally, factors contributing to catalyst deactivation are discussed. Finally, the review addresses current technical challenges and offers future perspectives on the development of catalysts with improved HDO activity and stability.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3375-3397"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676159","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}

{"title":"Visible-light-induced photoredox-catalyzed dearomative dicarboxylation of arenes using formate and CO2†","authors":"Jiayuan Li ,&nbsp;Zeyu Zhang ,&nbsp;Yaping Yi ,&nbsp;Chanjuan Xi","doi":"10.1039/d5gc00240k","DOIUrl":"10.1039/d5gc00240k","url":null,"abstract":"<div><div>The visible-light-induced photoredox-catalyzed dearomative dicarboxylation of polycyclic arenes and heteroarenes using formate and CO₂ was achieved. This reaction was performed under mild conditions to obtain dearomative dicarboxylative products with high selectivity and good yields. Mechanism experiments were performed to demonstrate that formate enabled the reaction to proceed <em>via</em> the carbon dioxide radical anion (CO₂˙⁻), which could be employed as a potent single-electron transfer (SET) reagent for the direct reduction of stable arenes under visible-light conditions.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 13","pages":"Pages 3443-3450"},"PeriodicalIF":9.3,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676181","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}