Polyester waste in the environment threatens public health and environmental ecosystems. Chemical recycling of polyester waste offers a dual solution to ensure resource sustainability and ecological restoration. This minireview highlights the traditional recycling methods and novel recycling strategies of polyester plastics. The conventional strategy includes pyrolysis, carbonation, and solvolysis of polyesters for degradation and recycling. Furthermore, the review delves into exploring emerging technologies including hydrogenolysis, electrocatalysis, photothermal, photoreforming, and enzymatic for upcycling polyesters. It emphasizes the selectivity of products during the polyester conversion process and elucidates conversion pathways. More importantly, the separation and purification of the products, the life cycle assessment, and the economic analysis of the overall recycling process are essential for evaluating the environmental and economic viability of chemical recycling of waste polyester plastics. Finally, the review offers perspective into the future challenges and developments of chemical recycling in the polyester economy.
{"title":"Circular Economy and Chemical Conversion for Polyester Wastes.","authors":"Jingjing Cao, Xin Qiu, Fan Zhang, Shaohai Fu","doi":"10.1002/cssc.202402100","DOIUrl":"https://doi.org/10.1002/cssc.202402100","url":null,"abstract":"<p><p>Polyester waste in the environment threatens public health and environmental ecosystems. Chemical recycling of polyester waste offers a dual solution to ensure resource sustainability and ecological restoration. This minireview highlights the traditional recycling methods and novel recycling strategies of polyester plastics. The conventional strategy includes pyrolysis, carbonation, and solvolysis of polyesters for degradation and recycling. Furthermore, the review delves into exploring emerging technologies including hydrogenolysis, electrocatalysis, photothermal, photoreforming, and enzymatic for upcycling polyesters. It emphasizes the selectivity of products during the polyester conversion process and elucidates conversion pathways. More importantly, the separation and purification of the products, the life cycle assessment, and the economic analysis of the overall recycling process are essential for evaluating the environmental and economic viability of chemical recycling of waste polyester plastics. Finally, the review offers perspective into the future challenges and developments of chemical recycling in the polyester economy.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.
金属中心的酸碱微环境对于构建先进的氧进化反应(OER)电催化剂至关重要。然而,对于钴基催化剂来说,酸性位点与 OER 性能之间的相关性仍不清楚。本文采用阳离子交换策略合成了空心植酸钴微多面体(M-CoPA,M = Cu、Sr)中的路易斯酸位点,并对其 OER 性能进行了系统研究。实验结果表明,路易斯酸性较强的 Cu2+ 位点在碱性电解质中表现出优异的内在活性和长期稳定性。光谱和电化学研究表明,中空植酸钴微多面体中的路易斯酸位点可以调节相邻钴中心的电子分布,进一步优化含氧物种的吸附强度。这项研究阐明了路易斯酸位点对 OER 动力学的影响,为开发能量转换系统的高效电催化剂提供了有效途径。
{"title":"Lewis acid sites in hollow cobalt phytate micropolyhedra promote the electrocatalytic water oxidation.","authors":"Mingxing Chen, Jing Qi, Qizhen Chen, Ying Gao, Yajing Zhao, Shengbo Gao, Enbo Shangguan","doi":"10.1002/cssc.202401932","DOIUrl":"https://doi.org/10.1002/cssc.202401932","url":null,"abstract":"<p><p>The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Advancing lithium-sulfur battery technology requires addressing both extrinsic cell-fabrication and intrinsic material challenges to improve efficiency, cyclability, and environmental sustainability. A key challenge is the low conductivity of sulfur cathodes, which is typically managed by incorporating conductive carbon materials. These materials enhance the performance of sulfur cathodes by facilitating high sulfur loading and improving polysulfide retention. In line with green chemistry principles and circular economy concepts, this study explores the use of recycled materials-specifically recycled quartz and board-as substrates for graphene coatings in lithium-sulfur cells. Recycled quartz bricks and blocks, predominantly SiO2, and recycled shelf boards, rich in Al2O3, are successfully coated with graphene, which significantly improves polysulfide adsorption and overall battery performance. The graphene-coated quartz exhibits high sulfur loading (8 mg cm-2), exceptional charge-storage capacity (1,114 mA·h g-1), and long cycle stability (200 cycles) with an energy density of 19 mW·h cm-2. This approach enhances the electrochemical performance of the lithium-sulfur cells and also aligns with sustainability goals by repurposing waste materials and minimizing environmental impact. This novel methodology demonstrates that integrating recycled materials can effectively address key challenges in lithium-sulfur battery technology, advancing both performance and environmental sustainability.
{"title":"Enhanced Performance of Lithium-Sulfur Batteries Using Construction Wastes: A Sustainable Approach to High-Loading Sulfur Cathodes.","authors":"Yi-Chen Huang, Cheng-Che Wu, Sheng-Heng Chung","doi":"10.1002/cssc.202402206","DOIUrl":"10.1002/cssc.202402206","url":null,"abstract":"<p><p>Advancing lithium-sulfur battery technology requires addressing both extrinsic cell-fabrication and intrinsic material challenges to improve efficiency, cyclability, and environmental sustainability. A key challenge is the low conductivity of sulfur cathodes, which is typically managed by incorporating conductive carbon materials. These materials enhance the performance of sulfur cathodes by facilitating high sulfur loading and improving polysulfide retention. In line with green chemistry principles and circular economy concepts, this study explores the use of recycled materials-specifically recycled quartz and board-as substrates for graphene coatings in lithium-sulfur cells. Recycled quartz bricks and blocks, predominantly SiO2, and recycled shelf boards, rich in Al2O3, are successfully coated with graphene, which significantly improves polysulfide adsorption and overall battery performance. The graphene-coated quartz exhibits high sulfur loading (8 mg cm-2), exceptional charge-storage capacity (1,114 mA·h g-1), and long cycle stability (200 cycles) with an energy density of 19 mW·h cm-2. This approach enhances the electrochemical performance of the lithium-sulfur cells and also aligns with sustainability goals by repurposing waste materials and minimizing environmental impact. This novel methodology demonstrates that integrating recycled materials can effectively address key challenges in lithium-sulfur battery technology, advancing both performance and environmental sustainability.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tiago G Paiva, Maykel Klem, Sara L Silvestre, João Coelho, Neri Alves, Elvira Fortunato, Eurico Cabrita, Marta C Corvo
Gel polymer electrolytes (GPEs) are regarded as a promising alternative to conventional electrolytes, combining the advantages of solid and liquid electrolytes. Leveraging the abundance and eco-friendliness of cellulose-based materials, GPEs were produced using methyl cellulose and incorporating various doping agents, either an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr14][TFSI]), its polymeric ionic liquid analogue (Poly(diallyldimethylammonium bis(trifluoromethylsulfonyl)imide) [PDADMA][TFSI]), or an anionically charged backbone polymeric ionic liquid (lithium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino) sulfonyl) imide] LiP[STFSI]). The ion dynamics and molecular interactions within the GPEs were thoroughly analyzed using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR), Heteronuclear Overhauser Enhancement Spectroscopy (HOESY), and Pulsed-Field Gradient Nuclear Magnetic Resonance Diffusion (PFG-NMR). Li+ transference numbers (tLi+) were successfully calculated. Our study found that by combining slow-diffusing polymeric ionic liquids (PILs) with fast-diffusing lithium salt, we were able to achieve transference numbers comparable to those of liquid electrolytes, especially with the anionic PIL, LiP[STFSI]. This research highlights the influence of the polymer's nature on lithium-ion transport within GPEs. Additionally, micro supercapacitor (MSC) devices assembled with these GPEs exhibited capacitive behavior. These findings suggest that further optimization of GPE composition could significantly improve their performance, thereby positioning them for application in sustainable and efficient energy storage systems.
{"title":"Poly(ionic) Liquid-Enhanced Ion Dynamics in Cellulose-Derived Gel Polymer Electrolytes.","authors":"Tiago G Paiva, Maykel Klem, Sara L Silvestre, João Coelho, Neri Alves, Elvira Fortunato, Eurico Cabrita, Marta C Corvo","doi":"10.1002/cssc.202401710","DOIUrl":"https://doi.org/10.1002/cssc.202401710","url":null,"abstract":"<p><p>Gel polymer electrolytes (GPEs) are regarded as a promising alternative to conventional electrolytes, combining the advantages of solid and liquid electrolytes. Leveraging the abundance and eco-friendliness of cellulose-based materials, GPEs were produced using methyl cellulose and incorporating various doping agents, either an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr14][TFSI]), its polymeric ionic liquid analogue (Poly(diallyldimethylammonium bis(trifluoromethylsulfonyl)imide) [PDADMA][TFSI]), or an anionically charged backbone polymeric ionic liquid (lithium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino) sulfonyl) imide] LiP[STFSI]). The ion dynamics and molecular interactions within the GPEs were thoroughly analyzed using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR), Heteronuclear Overhauser Enhancement Spectroscopy (HOESY), and Pulsed-Field Gradient Nuclear Magnetic Resonance Diffusion (PFG-NMR). Li+ transference numbers (tLi+) were successfully calculated. Our study found that by combining slow-diffusing polymeric ionic liquids (PILs) with fast-diffusing lithium salt, we were able to achieve transference numbers comparable to those of liquid electrolytes, especially with the anionic PIL, LiP[STFSI]. This research highlights the influence of the polymer's nature on lithium-ion transport within GPEs. Additionally, micro supercapacitor (MSC) devices assembled with these GPEs exhibited capacitive behavior. These findings suggest that further optimization of GPE composition could significantly improve their performance, thereby positioning them for application in sustainable and efficient energy storage systems.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589661","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shusheng Jiang, Miao Wang, Yahao Huang, Jinglan Wen, Peng Hu
Plastic pollution poses a significant challenge to environmental conservation. Efficient recycling of plastic is a key strategy to address this issue. Polyethylene terephthalate (PET), commonly found in plastic bottles, represents a substantial portion of plastic waste. Consequently, the efficient degradation and recycling of PET is crucial for the sustainable development of society. However, the implementation of methods for PET depolymerization and recycling typically necessitates alkaline/acidic pre-treatment and significant energy input for heating. Here, we propose a gentle, and highly efficient photocatalysis approach for selectively degrading PET plastic waste into terephthalic acid (TPA) in high yield (up to 99%) using cost-effective iron salts. Notably, this method achieved excellent selectivity with high TON and TOF values, applying oxygen or air as environmentally friendly oxidants. In addition, the solvent can be recycled without compromising the TPA yield, and large-scale reactions can be performed smoothly.
塑料污染对环境保护构成了重大挑战。高效回收塑料是解决这一问题的关键策略。塑料瓶中常见的聚对苯二甲酸乙二醇酯(PET)占塑料垃圾的很大一部分。因此,有效降解和回收 PET 对社会的可持续发展至关重要。然而,PET 解聚和回收方法的实施通常需要碱/酸预处理和大量的加热能源投入。在此,我们提出了一种温和、高效的光催化方法,利用具有成本效益的铁盐选择性地将 PET 塑料废料高产率(高达 99%)降解为对苯二甲酸(TPA)。值得注意的是,这种方法在使用氧气或空气作为环保氧化剂的情况下,实现了极佳的选择性和较高的 TON 值和 TOF 值。此外,溶剂可以循环使用,而不会影响 TPA 收率,大规模反应也能顺利进行。
{"title":"Selective Degradation of Polyethylene Terephthalate Plastic Waste Using Iron Salt Photocatalysts.","authors":"Shusheng Jiang, Miao Wang, Yahao Huang, Jinglan Wen, Peng Hu","doi":"10.1002/cssc.202401920","DOIUrl":"https://doi.org/10.1002/cssc.202401920","url":null,"abstract":"<p><p>Plastic pollution poses a significant challenge to environmental conservation. Efficient recycling of plastic is a key strategy to address this issue. Polyethylene terephthalate (PET), commonly found in plastic bottles, represents a substantial portion of plastic waste. Consequently, the efficient degradation and recycling of PET is crucial for the sustainable development of society. However, the implementation of methods for PET depolymerization and recycling typically necessitates alkaline/acidic pre-treatment and significant energy input for heating. Here, we propose a gentle, and highly efficient photocatalysis approach for selectively degrading PET plastic waste into terephthalic acid (TPA) in high yield (up to 99%) using cost-effective iron salts. Notably, this method achieved excellent selectivity with high TON and TOF values, applying oxygen or air as environmentally friendly oxidants. In addition, the solvent can be recycled without compromising the TPA yield, and large-scale reactions can be performed smoothly.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the quest for sustainable hydrogen production, the use of biomass-derived feedstock is gaining importance. Acceptorless Dehydrogenation (AD) in the presence of efficient and selective catalysts has been explored worldwide as a suitable method to produce hydrogen from hydrogen-rich simple organic molecules. Among these, glycerol and sugars have the advantage of being cheap, abundant, and obtainable from fatty acid basic hydrolysis (biodiesel industry) and from biomass by biochemical and thermochemical processing, respectively. Although heterogeneous catalysts are more widely used for hydrogen production from biomass-based feedstock, the harsh reaction conditions applied limit applicability due to deactivation of active sites due to coking of carbonaceous materials. Moreover, heterogeneous catalyst are more difficult to fine-tune than homogeneous counterparts, and the latter also allow for high process selectivities under milder conditions. The present Concept article summarizes the main features of the most active homogeneous catalysts reported for glycerol and monosaccharides AD. In order to directly compare hydrogen production efficiencies, the choice of literature works was limited to reports where hydrogen was clearly quantified by yields and turnover numbers (TONs). The types of transition metals and ligands is discussed, together with a perspective view on future challenges of homogeneous AD reactions for practical applications.
在寻求可持续制氢的过程中,生物质原料的使用正变得越来越重要。在高效和选择性催化剂的作用下,无受体脱氢(AD)作为一种从富氢简单有机分子制氢的合适方法,已在全球范围内得到探索。其中,甘油和糖具有廉价、丰富的优势,可分别从脂肪酸基础水解(生物柴油工业)和生物质中通过生化和热化学处理获得。虽然异相催化剂更广泛地用于以生物质为原料制氢,但由于碳质材料结焦导致活性位点失活,因此苛刻的反应条件限制了其适用性。此外,与均相催化剂相比,异相催化剂更难进行微调,而均相催化剂还能在较温和的条件下实现较高的工艺选择性。本概念文章总结了已报道的用于甘油和单糖 AD 的最活跃均相催化剂的主要特点。为了直接比较制氢效率,对文献作品的选择仅限于通过产率和周转次数(TONs)对氢进行明确量化的报告。本文讨论了过渡金属和配体的类型,并展望了均相 AD 反应在实际应用中的未来挑战。
{"title":"Sustainable Hydrogen Production by Glycerol and Monosaccharides Catalytic Acceptorless Dehydrogenation (AD) in Homogeneous Phase.","authors":"Sylwia Kostera, Luca Gonsalvi","doi":"10.1002/cssc.202400639","DOIUrl":"https://doi.org/10.1002/cssc.202400639","url":null,"abstract":"<p><p>In the quest for sustainable hydrogen production, the use of biomass-derived feedstock is gaining importance. Acceptorless Dehydrogenation (AD) in the presence of efficient and selective catalysts has been explored worldwide as a suitable method to produce hydrogen from hydrogen-rich simple organic molecules. Among these, glycerol and sugars have the advantage of being cheap, abundant, and obtainable from fatty acid basic hydrolysis (biodiesel industry) and from biomass by biochemical and thermochemical processing, respectively. Although heterogeneous catalysts are more widely used for hydrogen production from biomass-based feedstock, the harsh reaction conditions applied limit applicability due to deactivation of active sites due to coking of carbonaceous materials. Moreover, heterogeneous catalyst are more difficult to fine-tune than homogeneous counterparts, and the latter also allow for high process selectivities under milder conditions. The present Concept article summarizes the main features of the most active homogeneous catalysts reported for glycerol and monosaccharides AD. In order to directly compare hydrogen production efficiencies, the choice of literature works was limited to reports where hydrogen was clearly quantified by yields and turnover numbers (TONs). The types of transition metals and ligands is discussed, together with a perspective view on future challenges of homogeneous AD reactions for practical applications.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"CORRIGENDUM: Correction to Solid State Zinc and Aluminum Ion Batteries: Challenges and Opportunities.","authors":"","doi":"10.1002/cssc.202401926","DOIUrl":"https://doi.org/10.1002/cssc.202401926","url":null,"abstract":"","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Emir Ardalı, Hadi Jahangiri, Navid Solati, Ugur Yahsi, Cumali Tav, Alphan Sennaroglu, Sarp Kaya
In this study, the ultrafast transport dynamics of the valence band hole states in CuBi2O4 (CBO) photocathodes were investigated by varying the atomic composition and manipulating their p-type character. As a comprehensive ultrafast optical transient absorption spectroscopy (TAS) investigation of compositionally manipulated CBO that combines both ex situ and in situ TAS experiments with photoelectrochemical (PEC) performance tests, the study reveals the polaron formation tendencies of the valence band (VB) holes at cationic vacancy sites. Therefore, it draws a complete picture of the ultrafast hole transport dynamics and provides valuable insights into the hindrance of the photocurrent generated in CBO.
本研究通过改变 CuBi2O4(CBO)光电阴极的原子成分并操纵其 p 型特性,研究了其价带空穴态的超快传输动力学。该研究结合了原位和非原位瞬态吸收光谱实验以及光电化学(PEC)性能测试,是对经过成分处理的 CBO 进行的一次全面的超快光学瞬态吸收光谱(TAS)研究,揭示了阳离子空位处价带(VB)空穴的极子形成趋势。因此,它描绘了超快空穴传输动力学的全貌,并为了解 CBO 中产生的光电流的阻碍因素提供了宝贵的见解。
{"title":"Cation Vacancy-Mediated Ultrafast Hole Transport in CuBi2O4 Photocathodes.","authors":"Emir Ardalı, Hadi Jahangiri, Navid Solati, Ugur Yahsi, Cumali Tav, Alphan Sennaroglu, Sarp Kaya","doi":"10.1002/cssc.202401345","DOIUrl":"https://doi.org/10.1002/cssc.202401345","url":null,"abstract":"<p><p>In this study, the ultrafast transport dynamics of the valence band hole states in CuBi2O4 (CBO) photocathodes were investigated by varying the atomic composition and manipulating their p-type character. As a comprehensive ultrafast optical transient absorption spectroscopy (TAS) investigation of compositionally manipulated CBO that combines both ex situ and in situ TAS experiments with photoelectrochemical (PEC) performance tests, the study reveals the polaron formation tendencies of the valence band (VB) holes at cationic vacancy sites. Therefore, it draws a complete picture of the ultrafast hole transport dynamics and provides valuable insights into the hindrance of the photocurrent generated in CBO.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tobias Heinks, Katrin Hofmann, Simon Last, Igor Gamm, Luise Blach, Ren Wei, Uwe T Bornscheuer, Christof Hamel, Jan von Langermann
Over the past years, enzymatic depolymerization of PET, one of the most widely used plastics worldwide, has become very efficient leading to the end products terephthalic acid (TPA) and ethylene glycol (EG) used for PET re-synthesis. Potent alternatives to these monomers are the intermediates BHET and MHET, the mono- and di-esters of TPA and EG which avoid total hydrolysis and can serve as single starting materials for direct re-polymerization. This study therefore aimed to selectively prepare those intermediates through reaction medium engineering during the biocatalytic hydrolysis of PET. After a comparative pre-screening of 12 PET-hydrolyzing enzymes, two of them (LCCICCG, IsPETasewt) were chosen for detailed investigations. Depending on the reaction conditions, MHET and BHET are predominantly obtainable: (i) MHET was produced in a better ratio and high concentrations at the beginning of the reaction when IsPETasewt and 10% EG was used; (ii) BHET was produced as predominant product when LCCICCG and 25% EG was used. TPA itself was nearly the single product at pH 9.0 after 24 h due to the self-hydrolysis of MHET and BHET under basic conditions. Using medium engineering in biocatalytic PET-hydrolysis, the product profile can be adjusted so that TPA, MHET or BHET is predominantly produced.
{"title":"Selective Modification of the Product Profile of Biocatalytic Hydrolyzed PET via Product-specific Medium Engineering.","authors":"Tobias Heinks, Katrin Hofmann, Simon Last, Igor Gamm, Luise Blach, Ren Wei, Uwe T Bornscheuer, Christof Hamel, Jan von Langermann","doi":"10.1002/cssc.202401759","DOIUrl":"https://doi.org/10.1002/cssc.202401759","url":null,"abstract":"<p><p>Over the past years, enzymatic depolymerization of PET, one of the most widely used plastics worldwide, has become very efficient leading to the end products terephthalic acid (TPA) and ethylene glycol (EG) used for PET re-synthesis. Potent alternatives to these monomers are the intermediates BHET and MHET, the mono- and di-esters of TPA and EG which avoid total hydrolysis and can serve as single starting materials for direct re-polymerization. This study therefore aimed to selectively prepare those intermediates through reaction medium engineering during the biocatalytic hydrolysis of PET. After a comparative pre-screening of 12 PET-hydrolyzing enzymes, two of them (LCCICCG, IsPETasewt) were chosen for detailed investigations. Depending on the reaction conditions, MHET and BHET are predominantly obtainable: (i) MHET was produced in a better ratio and high concentrations at the beginning of the reaction when IsPETasewt and 10% EG was used; (ii) BHET was produced as predominant product when LCCICCG and 25% EG was used. TPA itself was nearly the single product at pH 9.0 after 24 h due to the self-hydrolysis of MHET and BHET under basic conditions. Using medium engineering in biocatalytic PET-hydrolysis, the product profile can be adjusted so that TPA, MHET or BHET is predominantly produced.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ke Yuan, Hong Li, Xindi Gu, Yalei Zheng, Xiaodong Wu, Yihe Zhao, Jiejie Zhou, Sheng Cui
Hydrogen peroxide (H2O2) is a widely used strong oxidant, and its traditional preparation methods, anthraquinone method, and direct synthesis method, have many drawbacks. The method of producing H2O2 by two-electron oxygen reduction reaction (2e- ORR) is considered an alternative strategy for the traditional anthraquinone method due to its high efficiency, energy saving, and environmental friendliness, but it remains a big challenge. In this review, we have described the mechanism of ORR and the principle of electrocatalytic performance testing, and have summarized the standard performance evaluation techniques for electrocatalysts to produce H2O2. Secondly, according to the theoretical calculation and experimental results, several kinds of efficient electrocatalysts are introduced. It is concluded that noble metal-based materials, carbon-based materials, non-noble metal composites, and single-atom catalysts are the preferred catalyst materials for the preparation of H2O2 by 2e- ORR. Finally, the advantages and novelty of 2e- ORR compared with traditional methods for H2O2 production, as well as the advantages and disadvantages of the above-mentioned high-efficiency catalysts, are summarized. The application prospect and development direction of high-efficiency catalysts for H2O2 production by 2e- ORR has been prospected, which is of great significance for promoting the electrochemical yield of H2O2 and developing green chemical production.
{"title":"Electrocatalysts for the Formation of Hydrogen Peroxide by Oxygen Reduction Reaction.","authors":"Ke Yuan, Hong Li, Xindi Gu, Yalei Zheng, Xiaodong Wu, Yihe Zhao, Jiejie Zhou, Sheng Cui","doi":"10.1002/cssc.202401952","DOIUrl":"10.1002/cssc.202401952","url":null,"abstract":"<p><p>Hydrogen peroxide (H2O2) is a widely used strong oxidant, and its traditional preparation methods, anthraquinone method, and direct synthesis method, have many drawbacks. The method of producing H2O2 by two-electron oxygen reduction reaction (2e- ORR) is considered an alternative strategy for the traditional anthraquinone method due to its high efficiency, energy saving, and environmental friendliness, but it remains a big challenge. In this review, we have described the mechanism of ORR and the principle of electrocatalytic performance testing, and have summarized the standard performance evaluation techniques for electrocatalysts to produce H2O2. Secondly, according to the theoretical calculation and experimental results, several kinds of efficient electrocatalysts are introduced. It is concluded that noble metal-based materials, carbon-based materials, non-noble metal composites, and single-atom catalysts are the preferred catalyst materials for the preparation of H2O2 by 2e- ORR. Finally, the advantages and novelty of 2e- ORR compared with traditional methods for H2O2 production, as well as the advantages and disadvantages of the above-mentioned high-efficiency catalysts, are summarized. The application prospect and development direction of high-efficiency catalysts for H2O2 production by 2e- ORR has been prospected, which is of great significance for promoting the electrochemical yield of H2O2 and developing green chemical production.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}