Le Zhou, Xianzhi Meng, Weiwei Li, Jiali Yu, Christian O. Kemefa, Susie Y. Dai, Arthur J. Ragauskas and Joshua S. Yuan
{"title":"Computational modeling-guided design of deep eutectic solvents for tailoring lignin chemistry during lignocellulose pretreatment†","authors":"Le Zhou, Xianzhi Meng, Weiwei Li, Jiali Yu, Christian O. Kemefa, Susie Y. Dai, Arthur J. Ragauskas and Joshua S. Yuan","doi":"10.1039/D4GC06120A","DOIUrl":"https://doi.org/10.1039/D4GC06120A","url":null,"abstract":"<p >Lignocellulosic biorefineries offer a sustainable approach to decarbonization and biofuel production, but the full utilization of biomass components, particularly lignin, remains a challenge due to its complex structure. Deep eutectic solvents (DESs) have emerged as promising green solvents for lignin extraction and structure regulation, offering chemical tunability, recyclability, and environmental benefits. However, their potential to precisely tailor lignin linkages during biomass pretreatment has been underexplored. In this study, we integrated computational modeling with experimental validation to design DESs for lignin property regulation and efficient delignification. A total of 260 DES candidates, comprising 13 hydrogen bond acceptors (HBAs), 20 hydrogen bond donors (HBDs), and 4 lignin dimer and 4 lignin carbohydrate complex models, were screened to predict activity coefficients (<em>γ</em>), focusing on their effects on β-O-4 and β-5 linkages in using the Conductor-like Screening Model for Real Solvents (COSMO-RS). Nine representative DESs were synthesized and tested with hardwood pretreatment. The results showed that smaller <em>γ</em> values indicate stronger degradation of β-O-4 and β-5 linkages, with both the HBD and HBA playing a significant role in delignification. The β-O-4 linkage is a critical determinant of lignin's properties and applications in value-added biomaterials. Multivariate analysis reveals the overall impact of lignin structures on β-O-4 and β-5 by accounting for interactions between variables, highlighting the importance of a multivariate approach. Incorporating model compounds with etherified phenol structures and lignin–carbohydrate complexes provided a more comprehensive calculation representation of the delignification process. Experimental validation demonstrated that the 1,8-diazabicyclo[5.4.0]undec-7-ene: lactic acid DES extracted lignin with a high β-O-4 content (47%), suitable for producing carbon fibers with superior mechanical properties. In contrast, a choline chloride: lactic acid DES completely cleaved β-O-4 linkages (0%), yielding uniform lignin nanoparticles with an enhanced zeta potential. These DESs also achieved effective delignification, allowing carbohydrates to be used for biofuels. This research establishes a computational modeling-guided framework for designing DESs to achieve controllable lignin linkage profiles, optimizing both delignification efficiency and material properties. The findings provide a pathway for enhancing the economic and environmental sustainability of lignocellulosic biorefineries and expand the applications of lignin in diverse, high-value biomaterials.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6260-6271"},"PeriodicalIF":9.3,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06120a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140055","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}
Arna Ganguly, Pingping Sun, Xinyu Liu, Hernan E. Delgado, Lili Sun and Amgad Elgowainy
{"title":"Techno-economic and life cycle analysis of bio-hydrogen production using bio-based waste streams through the integration of dark fermentation and microbial electrolysis†","authors":"Arna Ganguly, Pingping Sun, Xinyu Liu, Hernan E. Delgado, Lili Sun and Amgad Elgowainy","doi":"10.1039/D4GC05020G","DOIUrl":"https://doi.org/10.1039/D4GC05020G","url":null,"abstract":"<p >Hydrogen derived from bio-based sources, or biohydrogen (bioH<small><sub>2</sub></small>), has the potential to reduce GHG emissions from industrial and transportation sectors, owing to the low carbon footprint and myriad applications like refinery operation, ammonia production, steel production, fuel cell, <em>etc.</em> To evaluate the commercialization potential of bioH<small><sub>2</sub></small> production, we modeled bioH<small><sub>2</sub></small> production and conducted techno-economic analysis (TEA) and life cycle analysis (LCA) of two facilities producing 50 metric tonnes of bioH<small><sub>2</sub></small> per day from cheese whey (CW) and solid food waste (SFW) through the integration of dark fermentation (DF) and microbial electrolysis cell (MEC) technologies. LCA results showed that CW and SFW can produce carbon-negative bioH<small><sub>2</sub></small>, with emissions of −8.6 and −8.0 kg GHG kg<small><sup>−1</sup></small> bioH<small><sub>2</sub></small> with carbon sequestration and renewable electricity resources, respectively, making bioH<small><sub>2</sub></small> potentially eligible for a tax credit of $3 kg<small><sup>−1</sup></small> H<small><sub>2</sub></small> based on provision 45 V of the U.S. Inflation Reduction Act (IRA). In this study, bioH<small><sub>2</sub></small> production treats waste streams to generate fresh water, thus, potentially can receive waste water treatment fee that varies with regions. The MEC capital cost dominates the bioH<small><sub>2</sub></small> cost, which is mainly determined by current density. With a current density of 20 A m<small><sup>−2</sup></small>, the production cost for CW input varied between $17 and $24 kg<small><sup>−1</sup></small> bioH<small><sub>2</sub></small>, while that for SFW input ranged from $29 to $30 kg<small><sup>−1</sup></small> bioH<small><sub>2</sub></small> under different operating conditions, considering the 45 V tax credit, waste water treatment fee and production revenue. If the current density increases to 100 A m<small><sup>−2</sup></small>, the bioH<small><sub>2</sub></small> cost decreases to a range of $4.0–$6.9 for CW and $5–$6 for SFW scenarios. This study also shows that low-cost bioH<small><sub>2</sub></small> can be produced using CW waste stream as feedstock.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6213-6231"},"PeriodicalIF":9.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc05020g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140053","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}
Lingli Zhu, Jin Cao, Hongmin Yang, Dekui Shen, Haitao Hu and Mengjia Dou
{"title":"Highly efficient fabrication of lemon peel-derived carbon quantum dots for multicolor light-emitting diodes†","authors":"Lingli Zhu, Jin Cao, Hongmin Yang, Dekui Shen, Haitao Hu and Mengjia Dou","doi":"10.1039/D5GC01179E","DOIUrl":"https://doi.org/10.1039/D5GC01179E","url":null,"abstract":"<p >Biomass-derived carbon quantum dots (CQDs) have emerged as a promising sustainable alternative to conventional semiconductor quantum dots for light-emitting diode (LED) applications, offering distinct advantages in terms of renewability, low toxicity, and environmental friendliness. However, the efficient preparation of multicolor biomass-derived CQDs remains a critical challenge for practical implementation. In this study, lemon peel was screened as the optimal precursor from 26 types of agricultural and forestry residues, landscaping wastes, and food wastes. A green synthesis strategy involving hydrothermal carbonization coupled with controlled heteroatom doping was developed, which enabled the preparation of multicolor CQDs with superior photoluminescence properties. The synthesized CQDs exhibited tunable emission wavelengths (440–655 nm), high fluorescence quantum yields (4.98–35.58%), and exceptional photostability. High-efficiency LEDs were successfully fabricated by constructing a multilayer device structure using a mixture of multicolor biomass-derived CQDs and polymers. The CQD-based LEDs exhibited high color rendering indices (81.8–92.9) and a wide color temperature range (3912–6964 K) covering the visible spectrum while maintaining a decay rate below 30% over an operating lifetime of 11 832–12 815 h. This work not only provides a novel route for low-cost and sustainable synthesis of CQDs but also establishes theoretical and technical foundations for green electronic devices, accelerating the application of biomass resources in high-value optoelectronic devices.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6184-6195"},"PeriodicalIF":9.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139959","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}
Wenchao Zhu, Gonggang Liu, Jinbo Hu, Geng Su, Miaohua Liu, Xianjun Li and Binghui Xu
{"title":"Low-temperature molten salt ion regeneration strategy towards green and efficient spent graphite recycling†","authors":"Wenchao Zhu, Gonggang Liu, Jinbo Hu, Geng Su, Miaohua Liu, Xianjun Li and Binghui Xu","doi":"10.1039/D5GC00513B","DOIUrl":"https://doi.org/10.1039/D5GC00513B","url":null,"abstract":"<p >Recovering electrode materials from spent lithium-ion batteries (LIBs) is increasingly valued for resource conservation and environmental protection. Graphite is the dominant anode material for commercial LIBs. However, the spent graphite (SG) is often discarded or incinerated due to its low economic value, complexity of separation, and structural damage by extended use. This study demonstrates a green and efficient method to regenerate spent graphite by a molten salt ion-assisted thermal treatment in air atmosphere, from which a MSG sample can be obtained. During the thermal treatment, residual metal ions from the SG are substantially removed due to the rapid ion migration process, atomic-level mixing and high solubility in the molten salt environment. Meanwhile, structural imperfections in the sp<small><sup>3</sup></small>-hybridized carbons of graphite and the attached amorphous carbons are repaired by the low temperature oxidation process. Interestingly, abundant nanochannels and C<img>O bonds are introduced, which facilitate the intercalation/deintercalation process of Li<small><sup>+</sup></small> and provide increased active sites for lithium storage. Thus, the MSG sample demonstrated a significant improvement as an anode material for LIBs compared with commercial graphite (CG) and conventionally processed graphite (CPG). A high discharge capacity of up to 427.1 mA h g<small><sup>−1</sup></small> at 0.1 C could be delivered for the MSG sample, representing an increment of 141.4 mA h g<small><sup>−1</sup></small> compared with SG. Even at 2.0 C, a reversible capacity of 200.2 mA h g<small><sup>−1</sup></small> after 1000 cycles can be achieved for the MSG. This work offers a green and feasible approach for recycling SG materials, alleviating resource pressure and environmental hazards while being suitable for industrial applications.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6145-6155"},"PeriodicalIF":9.3,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139956","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}
Hannah R. Valentino, Liangyu Qian, Jerry M. Parks, Erin E. Drufva, Ada Sedova, Pankti S. Mehta, Mary P. Watson, Richard J. Giannone, Stephanie S. Galanie and Joshua K. Michener
{"title":"Engineered enzymatic cascade converts diols to amino alcohols†","authors":"Hannah R. Valentino, Liangyu Qian, Jerry M. Parks, Erin E. Drufva, Ada Sedova, Pankti S. Mehta, Mary P. Watson, Richard J. Giannone, Stephanie S. Galanie and Joshua K. Michener","doi":"10.1039/D4GC02141J","DOIUrl":"https://doi.org/10.1039/D4GC02141J","url":null,"abstract":"<p >Aliphatic amino alcohols such as 6-amino-1-hexanol are potential platform chemicals for a variety of advanced materials, but applications are currently limited by reagent costs. Aliphatic amino alcohols can currently be synthesized from biomass-derived diols at elevated temperatures and pressures using Ru-based catalysts that produce a mixture of amino-alcohol, diamine, and cyclic amine products. Replacing chemical amination with an enzymatic cascade would reduce resource needs and enable reactions under milder conditions. In this work, we characterized a two-enzyme cascade that selectively converts C4–C7 diols to the corresponding amino alcohols under aqueous conditions at room temperature and pressure. By engineering the rate-limiting enzyme and optimizing reaction conditions, we increased amino alcohol production nearly 30-fold, achieving a selectivity of 99%. The same enzyme cascade could also be used to convert amino alcohols into cyclic amines through reduction of the corresponding cyclic imine. This engineered cascade provides a green opportunity to sustainably synthesize asymmetric bifunctional platform chemicals.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6283-6292"},"PeriodicalIF":9.3,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc02141j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140033","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}
Rahul Daga Patil, Sandip Bapu Khatal, Manohar Shivaji Padmor and Sanjay Pratihar
{"title":"Waste-minimized, ecofriendly, and chemoselective room-temperature hydrogenation of CC bonds using a homogeneous recyclable imidazole-based Ru(ii)-p-cym catalyst†","authors":"Rahul Daga Patil, Sandip Bapu Khatal, Manohar Shivaji Padmor and Sanjay Pratihar","doi":"10.1039/D5GC01274K","DOIUrl":"https://doi.org/10.1039/D5GC01274K","url":null,"abstract":"<p >Catalytic hydrogenation of C<img>C bonds is crucial in fine chemical and pharmaceutical synthesis, yet the efficient recovery and reuse of homogeneous catalysts remain a challenge. Herein, we report a well-defined <strong>Ru-1</strong> catalyst derived from 2,2′-bisbenzimidazole (BiBzImH<small><sub>2</sub></small>) and Ru(<small>II</small>)-<em>para</em>-cymene, enabling chemoselective C<img>C hydrogenation at room temperature under moderate H<small><sub>2</sub></small> pressure without additives or base. <strong>Ru-1</strong> exhibits high turnover frequencies (TOFs), a broad substrate scope (61 examples), and remarkable functional group tolerance. Notably, <strong>Ru-1</strong> is 2 to 85 times more cost-effective than reported catalysts and can be efficiently recovered <em>via</em> solvent-mediated precipitation, maintaining its efficiency over multiple cycles. Mechanistic studies, including spectroscopic and isotopic labeling experiments, suggest that hydrogen activation requires vacant coordination sites at high pressure, proceeding without metal–ligand cooperativity. Moreover, the catalyst can be easily separated through solvent-mediated precipitation followed by product isolation through solvent evaporation without column chromatographic separation, minimizing solvent use and waste. Scalability and reusability studies confirm the practicality of this system, while green chemistry assessments (CHEM21 toolkit, <em>E</em>-factor, and EcoScale analysis) highlight its environmental sustainability.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6170-6183"},"PeriodicalIF":9.3,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139958","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":"Radical click reaction for C–S bond construction via reductive coupling of phthalimide derivatives†","authors":"Jia-Fan Qiao, Tian-Zhang Wang, Peng-Hui Shen, Yu-Qiu Guan, Ya-Xin Yu and Yu-Feng Liang","doi":"10.1039/D5GC01731A","DOIUrl":"https://doi.org/10.1039/D5GC01731A","url":null,"abstract":"<p >Click reactions have been highlighted as a powerful strategy for the rapid synthesis of chemicals, revolutionizing approaches in many fields in a short span of time with high reliability and efficiency. Herein, a novel method for a radical click reaction is presented for the synthesis of alkyl xanthates <em>via</em> the decarboxylative coupling of <em>N</em>-hydroxyphthalimide esters with <em>N</em>-xanthylphthalimides. This reductive cross-coupling was completed in 2 min at room temperature with simple operation. Primary, secondary and tertiary alkyl xanthate products were obtained in good yields without the need for a transition metal catalyst. This strategy was characterized by a broad scope encompassing common carboxylic acid and bioactive molecules, excellent functional group compatibility and rapid implementation. Mechanistic experiments demonstrated that the activation modes of the two phthalimide derivatives were independent yet proceeded through similar processes, and the product was efficiently generated <em>via</em> a coupling pathway between a persistent sulfur radical and a transient alkyl radical.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6272-6282"},"PeriodicalIF":9.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140032","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":"Tandem electrocatalytic benzylic alcohol oxidation and aldol condensation for efficient valuable α,β-unsaturated ketone production†","authors":"Yifan Yan, Xi Cai, Jiangrong Yang, Yu Fu, Qiwei Shi, Pengjie Hao, Hua Zhou, Zhenhua Li, Mingfei Shao and Haohong Duan","doi":"10.1039/D5GC01155H","DOIUrl":"https://doi.org/10.1039/D5GC01155H","url":null,"abstract":"<p >α,β-Unsaturated ketones, crucial in organic synthesis and life sciences, are conventionally produced through aldol condensation of ketones and aldehydes. However, traditional synthesis methods involve high temperature, pressure, and the use of environmentally harmful solvents, hindering sustainable development. Herein, we present one-step electrosynthesis of benzylidene acetones and 2-methylenephenyl cyclohexanone <em>via</em> tandem reactions, by coupling electrooxidation of benzylic alcohols to the corresponding aldehyde, followed by aldol condensation between the aldehyde and the ketone. Selective formation of benzaldehydes is key to the tandem reaction and was achieved over a cubic oxide-supported gold catalyst (Au/CuO) as the anode, showing the ability to adsorb benzylic alcohols and generate the active adsorbed oxygen species (OH*) for selective oxidation. The tandem reaction strategy demonstrates its versatility in the synthesis of α,β-unsaturated ketones from benzyl alcohols with different substituents and acetone/cyclohexanone. As proof of concept, we constructed a flow electrolyzer and achieved continuous electrosynthesis of benzylidene acetone coupled with H<small><sub>2</sub></small> production at ampere-level current, delivering a benzylidene acetone productivity of 9.5 mmol h<small><sup>−1</sup></small> and a H<small><sub>2</sub></small> productivity of 0.4 L h<small><sup>−1</sup></small>. This study demonstrates the potential of coupling electrocatalysis and thermocatalysis in tandem, with implications for synthesis of more value-added chemicals.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6016-6026"},"PeriodicalIF":9.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140000","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}
Yao Wang, Zhangpei Liu, Yongjun Feng, Christopher Hardacre, Sarayute Chansai and Zhiming Liu
{"title":"Boosting NH3-SCR of NOx performance through sustainable and economical synthesis of Cu-SAPO-34 zeolites from attapulgite†","authors":"Yao Wang, Zhangpei Liu, Yongjun Feng, Christopher Hardacre, Sarayute Chansai and Zhiming Liu","doi":"10.1039/D5GC01362C","DOIUrl":"https://doi.org/10.1039/D5GC01362C","url":null,"abstract":"<p >Small-pore Cu-SAPO-34 zeolites have been intensively studied for the selective catalytic reduction of nitrogen oxides (NO<small><sub><em>x</em></sub></small>) with NH<small><sub>3</sub></small>. However, the prohibitive cost of conventional synthesis has limited their widespread industrial application. Herein, nanosized Cu-SAPO-34-ATP has been synthesized from attapulgite (ATP) by a hydrothermal method, which is a green and economical route. The synthesized nanosized Cu-SAPO-34-ATP zeolites possess high crystallinity, uniform cubic morphology, enhanced acid sites, and abundant Cu-active species. The nanoscale architecture of Cu-SAPO-34-ATP catalysts significantly improves mass transport properties due to substantially reduced diffusion pathways. Consequently, compared to conventional Cu-SAPO-34, the Cu-SAPO-34-ATP zeolites exhibit excellent low-temperature NH<small><sub>3</sub></small>-SCR activity, along with enhanced hydrothermal stability. Notably, over the Cu<small><sub>0.05</sub></small>-SAPO-34-ATP catalyst more than 90% NO<small><sub><em>x</em></sub></small> conversion is achieved in the temperature range from 215 °C to 535 °C. These results highlight the potential of nanosized Cu-SAPO-34 derived from ATP as a next-generation deNO<small><sub><em>x</em></sub></small> catalyst, combining environmental and resource-recycling advantages. This study also offers insights for designing innovative nanocatalysts for air pollution control.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 6293-6305"},"PeriodicalIF":9.3,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140034","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}
Dan Wang, Yu-Xuan Bai, Zi-Xiang Zhou, Wei Cao, Yang-Min Ma and Chao Wang
{"title":"Towards ultra-stable aqueous zinc-ion batteries via electrochemical polymerization of phthalimido-anchored benzoquinone†","authors":"Dan Wang, Yu-Xuan Bai, Zi-Xiang Zhou, Wei Cao, Yang-Min Ma and Chao Wang","doi":"10.1039/D5GC01391G","DOIUrl":"https://doi.org/10.1039/D5GC01391G","url":null,"abstract":"<p >Designing organic cathode materials with high specific capacity and stability for aqueous zinc-ion batteries (ZIBs) is essential. Small organic molecules suffer from limited conductivity and high solubility, which hamper the charge storage performance of ZIBs. Here, tetra-(phthalimido)-benzoquinone (TPB), which has multiple carbonyl groups, is selected as a monomer for electropolymerization to fabricate polyTPB (PTPB)/carbon cloth (CC). Aqueous ZIBs with PTPB/CC demonstrate ultralong cycling stability, sustaining 30 000 galvanostatic charge–discharge cycles at 10 A g<small><sup>−1</sup></small>. The specific discharge capacity of the ZIB with PTPB/CC reaches 261 mA h g<small><sup>−1</sup></small> at a charge–discharge current density of 0.1 A g<small><sup>−1</sup></small>. Kinetic analysis demonstrates that charge storage is predominantly governed by surface capacitive-controlled processes. The charge storage mechanism is further probed through <em>ex situ</em> characterization studies. The carbonyl/hydroxyl and amino/imino groups are identified as the active groups for charge storage, and the redox process involves the insertion and extraction of both Zn<small><sup>2+</sup></small> and H<small><sup>+</sup></small>. Density functional theory calculations demonstrate that carbonyl oxygen atoms, acting as nucleophilic sites, preferentially bind Zn<small><sup>2+</sup></small> over H<small><sup>+</sup></small> due to a lower Gibbs free energy change (Δ<em>G</em>) and a higher Zn<small><sup>2+</sup></small> concentration in the electrolyte. The five-step Zn<small><sup>2+</sup></small>/2e<small><sup>−</sup></small> insertion pathway during discharging is validated to be thermodynamically viable.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 20","pages":" 5832-5843"},"PeriodicalIF":9.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144084847","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}