{"title":"Lignin-Assisted Photoreactions: Unveiling New Frontiers in Light-Induced Chemistry.","authors":"Hongda Guo, Xiongfei Luo, Luyao Wang, Chenhui Yang, Shujun Li, Shouxin Liu, Jian Li, Zhijun Chen","doi":"10.1002/cssc.202402117","DOIUrl":"10.1002/cssc.202402117","url":null,"abstract":"<p><p>Lignin, the most abundant aromatic biopolymer, is emerging as a mainstay of the upcoming revolution in sustainable materials processing. Despite the inherent challenges associated with the heterogeneous structure of lignin, significant progress has recently been made in developing innovative strategies to valorize this fascinating aromatic biopolymer to deliver industry-demanded products via photoreactions. The purpose of this concept article is to unravel insights into these creative approaches in lignin-assisted photoreactions, focusing on photopolymerization to construct functional polymeric materials and photoreduction to provide valuable chemicals, wherein lignin serves as a macromolecular photoinitiator and a reductive photocatalyst, respectively. The existing strategies for improving the photochemical quantum yield of lignin in photopolymerization and harnessing lignin macromolecules as photoresponsive polymers to facilitate electron transfer in photocatalytic reactions are also summarized. In the future, such photochemical lignin valorization concepts could potentially provide new possibilities for achieving a profitable value chain for integrated biorefinery processes.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402117"},"PeriodicalIF":7.5,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646224","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":"Photocatalytic Upcycling of Plastic Waste into Syngas by ZnS/Ga<sub>2</sub>O<sub>3</sub> Z-Scheme Heterojunction.","authors":"Tong Xu, Tao Shan, Yuting Jiang, Lian-Hua Xu, Huiyan Zhang, Sheng Chu","doi":"10.1002/cssc.202402310","DOIUrl":"10.1002/cssc.202402310","url":null,"abstract":"<p><p>The photocatalytic conversion of plastic waste into value-added products using solar energy presents a promising approach for promoting environmental sustainability. Nonetheless, the emission of CO<sub>2</sub> during the conventional photocatalytic degradation process remains a major hurdle that impedes its further development. In this study, we propose an efficient photocatalytic conversion of polyethylene plastic into syngas (CO+H<sub>2</sub> mixtures) by using a ZnS/Ga<sub>2</sub>O<sub>3</sub> Z-scheme heterojunction photocatalyst. It is found that the strong redox capability of photogenerated holes and electrons in the Z-scheme heterojunction photocatalyst can promote the oxidative depolymerization of PE plastic, concurrently enabling the efficient reduction of the intermediate product CO<sub>2</sub> into syngas. Furthermore, this system also demonstrates applicability in the conversion and upcycling of other polyolefin plastics including polypropylene and polyvinyl chloride. Our findings highlight the potential of polyolefin plastics photoreforming for the production of syngas under environmentally benign conditions.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402310"},"PeriodicalIF":7.5,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643541","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":"Crystallization of Cathode Active Material Precursors from Tartaric Acid Solution.","authors":"Chunyan Ma, Mona Mohamoud, Tiaan Punt, Jinlong Li, Michael Svärd, Kerstin Forsberg","doi":"10.1002/cssc.202401523","DOIUrl":"10.1002/cssc.202401523","url":null,"abstract":"<p><p>In this study L-(+)-tartaric acid was used to extract metals from either pure cathode material (NMC111) or black mass from spent lithium-ion batteries. The leaching efficiencies of Li, Co, Ni, and Mn from NMC111 are >87 % at 70 °C, with an initial solid to liquid ratio of 17, and >72.4±1.0 % from black mass under corresponding conditions. The metals tend to form mixed phases in antisolvent crystallization and seeding has a minimal effect on the final solid composition. Impurities influence both crystal nucleation and growth. By controlling the antisolvent addition rate crystal growth can be promoted. The theoretical dielectric constant of the solution is shown to correlate excellently to the recovery efficiency across different antisolvents, where a value <52 results in over 95 % total transition metal recovery efficiency. The correlation can be a powerful tool for quantitative prediction of optimal solvent composition for effective antisolvent crystallization.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401523"},"PeriodicalIF":7.5,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643540","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}
ChemSusChemPub Date : 2024-11-16DOI: 10.1002/cssc.202401606
Hong Ding, Ping Liu, Chengyu Liu, Tiantian Li, Wen Guo, Haijiao Xie, Gang Wang, Tiantian Gu
{"title":"Two-Dimensional π-d Conjugated Conductive Metal-Organic Framework with Triple Active Centers as High-Performance Cathodes for Flexible Zinc Batteries.","authors":"Hong Ding, Ping Liu, Chengyu Liu, Tiantian Li, Wen Guo, Haijiao Xie, Gang Wang, Tiantian Gu","doi":"10.1002/cssc.202401606","DOIUrl":"10.1002/cssc.202401606","url":null,"abstract":"<p><p>Conductive metal-organic frameworks (C-MOFs) have received extensive interest in high-performance zinc-ion batteries (ZIBs) owing to multi-redox sites and high electrical conductivity. Here, we present a π-d C-MOF by coordinating 2,3,5,6-tetraaminobenzoquinone (TABQ) ligands with Cu<sup>2+</sup> ions (2D Cu-TABQ) acting as cathodes for ZIBs. Benefiting from a triple active center (Cu<sup>2+</sup>, C=O, and C=N), 2D Cu-TABQ shows an ultra-high reversible capacity of 297.7 mAh g<sup>-1</sup> at 0.2 A g<sup>-1</sup>. Meanwhile, 2D Cu-TABQ also has superior cycle stability with a capacity of up to 98.2 mAh g<sup>-1</sup> after 1000 times at 2.0 A g<sup>-1</sup>. Considering the instability of the ligand bonds of C-MOFs in aqueous electrolytes, this work uses gel electrolytes to reduce the dissolution of organic ligands into the electrolyte, thus suppressing the shuttle effect, significantly improving the cycling stability of 2D Cu-TABQ. The flexible battery assembled by 2D Cu-TABQ shows excellent capacity retention (64.4 %) after 50 times at 0.2 A g<sup>-1</sup>, which is significantly better than 36.4 % in the common electrolyte, as well as outstanding bending resistance and electrochemical properties at different folding angles. This investigation will highlight the electrochemical application of C-MOFs in flexible zinc ion batteries and offer novel ideas for the structural design of cathodes with multiple active centers.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401606"},"PeriodicalIF":7.5,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643542","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}
ChemSusChemPub Date : 2024-11-15DOI: 10.1002/cssc.202401714
Bhanupriya Boruah, Juan A Lopez-Ruiz
{"title":"Progress on Photo-, Electro-, and Photoelectro-Catalytic Conversion of Recalcitrant Polyethylene, Polypropylene, and Polystyrene - A Review.","authors":"Bhanupriya Boruah, Juan A Lopez-Ruiz","doi":"10.1002/cssc.202401714","DOIUrl":"10.1002/cssc.202401714","url":null,"abstract":"<p><p>Recalcitrant waste plastics such a polyethylene, polypropylene, and polystyrene are difficult to recycle and are mostly disposed of in landfills and eventually leached into the environmental as micro- and nano-plastics. This review explores how photo-, electro-, and combined photoelectro-catalytic processes can assist in the degradation and upcycling of waste plastic into different chemicals and mitigate their release to the environment. In this work, we discuss how the different reaction mechanisms proceed, explore the current relevant literature, and highlight the developments needed to advance the field.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401714"},"PeriodicalIF":7.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637960","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}
ChemSusChemPub Date : 2024-11-15DOI: 10.1002/cssc.202402165
Mei Wu, Wenping Liu, Fengjuan Deng, Shima Liu, Ke Song, Xianwu Zhou, Jie Guo, Jian He, Hu Li
{"title":"Steering Acid-Base Site Distribution and Hydrophobicity of Bioresourced Bifunctional Hybrid Materials for Direct Synthesis of γ-Valerolactone from Biomass-Based Furfural.","authors":"Mei Wu, Wenping Liu, Fengjuan Deng, Shima Liu, Ke Song, Xianwu Zhou, Jie Guo, Jian He, Hu Li","doi":"10.1002/cssc.202402165","DOIUrl":"10.1002/cssc.202402165","url":null,"abstract":"<p><p>The direct production of value-added chemicals from biomass via multiple conversion processes with a sole renewable solid catalyst is promising for carbon-neutral development while challenging. Herein, a series of novel bioresourced organic-inorganic hybrid materials were synthesized from bio-based ascorbic acid (Vc), zirconium chloride (ZrCl<sub>4</sub>) and p-toluenesulfonic acid (p-TSA) through a facile solvothermal process. The as-prepared Zr-Vc-3 catalyst with Vc, ZrCl<sub>4</sub>, and p-TSA in the 1 : 1:0.5 molar ratio displayed outstanding performance in direct furfural-to-γ-valerolactone (GVL) transformation, giving an ultrahigh GVL yield of 76.2 %, with an ideal activation energy (55.46 kJ mol<sup>-1</sup>), outperforming state-of-the-art catalysts. The superior performance of Zr-Vc-3 could be ascribed to its good reusability, relatively large pore size, suitable amount of acid-base sites, and good hydrophobicity. Mechanistic studies unveiled that Lewis acid-base sites facilitate the conversion of furfural to furfuryl alcohol and isopropyl levulinate (IPL) to 4-hydroxypentanoate via transfer hydrogenation process, while Brønsted acid sites are instrumental in the ring-opening of furfuryl alcohol to IPL and the lactonization of 4-hydroxypentanoate to GVL, overall contributing to the multi-step conversion of furfural to GVL in a single pot. This work provides a valuable reference for precisely constructing bio-based OIHMs with tailored functionalities for the one-pot valorization of biomass feedstocks via tandem reactions.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402165"},"PeriodicalIF":7.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637961","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}
ChemSusChemPub Date : 2024-11-15DOI: 10.1002/cssc.202402027
Oleksandr Astakhov, Thérèse Cibaka, Lars Wieprecht, Uwe Rau, Tsvetelina Merdzhanova
{"title":"Unfolding Electrolyzer Characteristics to Reveal Solar-to-Chemical Efficiency Potential: Rapid Analysis Method Bridging Electrochemistry and Photovoltaics.","authors":"Oleksandr Astakhov, Thérèse Cibaka, Lars Wieprecht, Uwe Rau, Tsvetelina Merdzhanova","doi":"10.1002/cssc.202402027","DOIUrl":"10.1002/cssc.202402027","url":null,"abstract":"<p><p>Development of photovoltaic-electrochemical (PV-EC) systems for energy storage and industry decarbonization requires multidisciplinary collaborative efforts of different research groups from both photovoltaic and electrochemical research communities. Consequently, the evaluation of the solar-to-chemical or solar-to-fuel efficiency of a new electrolyzer (EC) as a part of a PV-EC system is a time-consuming task that is challenging in a routine optimization loop. To address this issue, a new rapid assessment method is proposed. This method employs power balance requirements to unfold the input EC characteristics into the parameter space of PV-EC systems. The system parameters, composed with the EC output characteristics, yield the solar-to-chemical efficiency attainable by the electrolyzer in combination with any PV device under any irradiance at any relative PV-to-EC scaling and any mode of power coupling. This comprehensive overview is achieved via a mathematically simple conversion of the EC characteristics in any spreadsheet software. The method, designed to streamline the development and minimize the efforts of both the photovoltaic and electrochemical communities, is demonstrated via the analysis of CO<sub>2</sub>-reduction electrolyzer characteristics and verified with dedicated PV-EC experiments.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402027"},"PeriodicalIF":7.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637962","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}
ChemSusChemPub Date : 2024-11-14DOI: 10.1002/cssc.202401803
Felix Nagler, Leonhard Kolb, Nino Christian, Andreas Flegler, Michael Hofmann, Guinevere A Giffin
{"title":"Influence of Process Conditions During Aqueous and Direct Recycling of NMC811 Cathodes.","authors":"Felix Nagler, Leonhard Kolb, Nino Christian, Andreas Flegler, Michael Hofmann, Guinevere A Giffin","doi":"10.1002/cssc.202401803","DOIUrl":"10.1002/cssc.202401803","url":null,"abstract":"<p><p>This study investigated the impact of various process conditions on the aqueous, direct recycling of LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> (NMC811) cathodes. Three model systems were used. The first system assumes that the current collector delamination is performed in a dry environment without the use of water as a process medium. Consequently, the NMC811 is only exposed to water during classification, where no aluminum foil is present. The second model system assumes that the current collector delamination occurs in water. Therefore, the NMC811 is exposed to water in the presence of aluminum foil. Due to the pH increase caused by the Li<sup>+</sup>/H<sup>+</sup> exchange reaction, the pH value surpasses the stability window of the aluminum-oxide passivation layer (pH 4.5-8.5), resulting in the deposition of aluminum-containing species on the NMC811 surface. The third model system is identical to the second, with the exception that H<sub>3</sub>PO<sub>4</sub> is added. This causes the pH to decrease and prevents corrosion of the aluminum foil. The findings reveal that process conditions significantly affect the surface chemistry on NMC811, influencing electrochemical performance. Notably, aluminum-containing species increase polarization. Heat treatment simulating regeneration led to cation mixing as surface species diffused into the NMC811 bulk structure, highlighting the need to control recycling process conditions.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401803"},"PeriodicalIF":7.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142611836","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}
ChemSusChemPub Date : 2024-11-14DOI: 10.1002/cssc.202401860
Shiyan Deng, Huiyao Li, Wenhao Tang, Youlan Zou, Shuang Deng
{"title":"ZnO Quantum Dots as PEO-Based Solid Electrolytes Fillers for Lithium Metal Batteries.","authors":"Shiyan Deng, Huiyao Li, Wenhao Tang, Youlan Zou, Shuang Deng","doi":"10.1002/cssc.202401860","DOIUrl":"https://doi.org/10.1002/cssc.202401860","url":null,"abstract":"<p><p>PEO-based solid polymer electrolyte (PEO SPE) is regarded as one of the most promising solid electrolytes due to its exceptional flexibility, cost-effectiveness, and ease of integration. However, its commercialization is hindered by inadequate ionic conductivity and unstable interface. By incorporating proper ZnO quantum-dots (QDs) fillers with enhanced surface activity, the ion transport inner the PEO-based electrolyte can be improved along with enhanced REDOX kinetics at the Li/PEO interface. The ionic conductivity reaches 5.97×10<sup>-4</sup> S cm<sup>-1</sup> at 60 °C. Moreover, ZnO QDs exhibit a quantum size effect and possess lithiophilic characteristics that promote uniform nucleation and redeposition of Li<sup>+</sup> while forming a stable Li-Zn alloy. This inhibits lithium dendrite formation and enhances the stability of Li anode. Li//Li cell with 3 % ZnO QDs works steadily for more than 2100 h at 60 °C with 0.1 mA cm<sup>-2</sup>. The assembled Li//LiFePO<sub>4</sub> cell provides a reversible capacity of 134.91 mAh g<sup>-1</sup> after200 cycles at 0.1 C.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401860"},"PeriodicalIF":7.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612717","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}
ChemSusChemPub Date : 2024-11-14DOI: 10.1002/cssc.202401350
Thamy L R Corrêa, Ellen K B Román, Carlos A R Costa, Lucia D Wolf, Richard Landers, Peter Biely, Mario T Murakami, Paul H Walton
{"title":"On the Non-Catalytic Role of Lytic Polysaccharide Monooxygenases in Boosting the Action of PETases on PET Polymers.","authors":"Thamy L R Corrêa, Ellen K B Román, Carlos A R Costa, Lucia D Wolf, Richard Landers, Peter Biely, Mario T Murakami, Paul H Walton","doi":"10.1002/cssc.202401350","DOIUrl":"https://doi.org/10.1002/cssc.202401350","url":null,"abstract":"<p><p>Synthetic polymers are resistant to biological attack, resulting in their long-term accumulation in landfills and in natural aquatic and terrestrial habitats. Lytic polysaccharide monooxygenases (LPMOs) are enzymes which oxidatively cleave the polysaccharide chains in recalcitrant polysaccharides such as cellulose. It has been widely hypothesised that LPMOs could be used to aid in the enzymatic breakdown of synthetic polymers. Herein, through the use of biochemical assays, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) we show that LPMOs can bind to polyethylene terephthalate (PET), and - in doing so - the hydrophobic surface of PET becomes more hydrophilic such that product release is boosted by subsequent treatment with classical PETases. The boosting effect is however, only observed in reactions when the LPMO and the PETase are added sequentially rather than simultaneously to the PET. Moreover, the same boosting effect is also seen when a catalytically-inactive mutant of LPMO is used, showing that the principal means by which AA9 LPMOs boost the degradation of synthetic polymers is through their role as a \"hydrophobin\" rather than as an oxygenase. Indeed, in accord with this role of LPMOs, we further show that this effect can be extended to other ostensibly 'non-catalytic' proteins beyond LPMOs, such as bovine serum albumin and lactate dehydrogenase.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401350"},"PeriodicalIF":7.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612517","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}