With the approaching of large-scale retirement of power lithium-ion batteries(LIBs),their urgent handling is required for environmental protection and resource reutilization.However,at present,substantial spent power ...With the approaching of large-scale retirement of power lithium-ion batteries(LIBs),their urgent handling is required for environmental protection and resource reutilization.However,at present,substantial spent power batteries,especially for those high recovery value cathode materials,have not been greenly,sustainably,and efficiently recycled.Compared to the traditional recovery method for cathode materials with high energy consumption and severe secondary pollution,the direct repair regeneration,as a new type of short-process and efficient treatment methods,has attracted widespread attention.However,it still faces challenges in homogenization repair,electrochemical performance decline,and scaling-up production.To promote the direct regeneration technology development of failed NCM materials,herein we deeply discuss the failure mechanism of nickel-cobalt-manganese(NCM)ternary cathode materials,including element loss,Li/Ni mixing,phase transformation,structural defects,oxygen release,and surface degradation and reconstruction.Based on this,the detailed analysis and summary of the direct regeneration method embracing solid-phase sintering,eutectic salt assistance,solvothermal synthesis,sol-gel process,spray drying,and redox mediation are provided.Further,the upcycling strategy for regeneration materials,such as single-crystallization and high-nickelization,structural regulation,ion doping,and surface engineering,are discussed in deep.Finally,the challenges faced by the direct regeneration and corresponding countermeasures are pointed out.Undoubtedly,this review provides valuable guidance for the efficient and high-value recovery of failed cathode materials.展开更多
Lithium-ion batteries(LIBs)are critical for the rapid growth of electric vehicles(EVs),but their inherent lifespan leads to numerous retirements and resource challenges.The efficacy of conventional recycling technique...Lithium-ion batteries(LIBs)are critical for the rapid growth of electric vehicles(EVs),but their inherent lifespan leads to numerous retirements and resource challenges.The efficacy of conventional recycling techniques is increasingly compromised by their high energy consumption and secondary pollution,rendering them less responsive to greener and more sustainable requirement of rapid development.Thus,the direct recycling process emerged and was considered as a more expedient and convenient method of recycling compared to the conventional recycling modes that are currently in study.However,due to the reliance on the indispensable sintering process,direct recycling still faces considerable challenges,motivating researchers to explore faster,greener,and more cost-effective strategies for LIBs recycling,Inspiringly,Joule heating recycling(JHR),an emerging technique,offers rapid,efficient impurity removal and material regeneration with minimal environmental impact,addressing limitations of existing methods.This method reduces the time for direct recycling of spent LIBs by a factor of at least three orders of magnitude and exhibits significant potential for future industrial production.Unfortunately,due to the lack of systematic organization and reporting,this next generation approach to direct recycling of spent LIBs has not yet gained much interest.To facilitate a more profound comprehension of rising flash recycling strategy,in this study,JHR is distinguished into two distinctive implementation pathways(including flash Joule heating and carbon thermal shock),designed to accommodate varying pretreatment stages and diverse spent LIBs materials.Subsequently,the advantages of the recently developed JHR of spent LIBs in terms of material performance,environmental friendliness,and economic viability are discussed in detail.Ultimately,with the goal of achieving more attractive society effects,the future direction of JHR of spent LIBs and its potential for practical application are proposed and envisaged.展开更多
Cold plasma-assisted catalytic upcycling of polyolefin wastes integrated with CO_(2)into value-added chemicals is a promising solution for mitigating the global carbon emissions and fossil energy crisis,but still chal...Cold plasma-assisted catalytic upcycling of polyolefin wastes integrated with CO_(2)into value-added chemicals is a promising solution for mitigating the global carbon emissions and fossil energy crisis,but still challenging due to the complexity of products and low energy efficiency.Given this,a novel one-stage process of cold plasma coupled with Ga-modified hierarchical H-ZSM-5(Ga/Hie-ZSM-5)catalyst for polyolefins upgrading was designed with polyolefins followed by the catalysts within the plasma region,which facilitated the upcycling of polyolefins to light olefins and CO_(2)activation by plasma,and thereby the enhanced synergy between cold plasma and catalysts for aromatics production.At an input power of ca.45 W without external heating,the low-density polyethylene(LDPE)waste was completely converted with the assistance of CO_(2)and the yield of oil products over the Ga/Hie-ZSM-5 catalyst was highly up to 62.2 wt%,with nearly 100% selectivity of aromatics.Meanwhile,the degradation efficiency of LDPE and the energy efficiency could reach 2.5 g_(LDPE)·g_(cat)^(-1)·h^(-1)and 55.56 g_(LDPE)·g_(cat)^(-1)·kW^(-1)h^(-1),respectively.Mechanism investigation revealed that the plasma and CO_(2)synergistically affect the primary cracking of LDPE,forming a primary product enriched in olefins and a small amount of CO.Subsequently,the produced olefins intermediates were further aromatized via cyclizationdehydrogenation route on the Ga/Hie-ZSM-5 catalyst with assistance of CO_(2)under the synergistic effect of plasma-catalysis.This work offers a feasible strategy to improve the yield of aromatic products for the plasma-catalytic upcycling of polyolefins and CO_(2)at ambient pressure without any external heating.展开更多
Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and ...Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and chemicals.However,studies on the depolymerization and functionalization of challenging super engineering plastics have remained in early stage and underexplored.In this review,we would like to discuss the representative accomplishments and mechanism insights on chemical protocols achieved in depolymerization of super engineering plastics,especially for poly(phenylene sulfide)(PPS),poly(aryl ether)s including poly(ether ether ketone)(PEEK),polysulfone(PSU),polyphenylsulfone(PPSU)and polyethersulfone(PES).We anticipate that this review will provide an overall perspective on the current status and future trends of this emerging field.展开更多
Polyvinyl chloride(PVC)is one of the most widely used plastic materials worldwide,particularly in long-life applications such as construction materials.However,recycling options for PVC waste remain limited,as convent...Polyvinyl chloride(PVC)is one of the most widely used plastic materials worldwide,particularly in long-life applications such as construction materials.However,recycling options for PVC waste remain limited,as conventional methods often degrade material quality or generate environmentally hazardous byproducts.In this study,we demonstrate an efficient process to convert PVC into new polymers with variable aromatic groups,using triethylsilane as the reductant in different solvents.This approach enables the production of polymers analogous to functionalized polyethylene(PE),which are typically challenging to obtain through conventional copolymerization or direct post-modification of C-H bonds in PE.The resulting polymers exhibit tunable thermal and mechanical properties depending on the introduced aromatic groups,which not only enhance the sustainable valorization of PVC waste,but also provide an opportunity for the synthesis of new functionalized polymers.展开更多
Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we construct...Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we constructed ultralow-coordinated Ni species with Ni–O coordination number of∼3 via a hydrothermal synthesis-sulfidation-annealing process and electrochemical activation and demonstrated the vital role in accelerating the proton deintercalation and reactive oxygen intermediate·OH formation during electro-reforming polyethylene terephthalate hydrolysate(POR).The target catalyst NiCoSx/NF afforded a high formate productivity of 7.4 mmol cm^(−2)h^(−1)at∼600 mA cm^(−2)with a formate Faradic efficiency(FE_(formate))of 92.4%in POR and maintained a FE_(formate)of∼90%for 100 h at 2 A in a membrane electrode assembly electrolyzer.Coupling POR on NiCoSx/NF with carbon dioxide reduction reaction on oxygen vacancies enriched Vo-BiSnO reached effective concurrent formate production with 172.7%of FE_(formate)at 500 mA cm^(−2)and long-term stability.Such excellent performance shows the great prospect of electrocatalyst design by regulating the local metal environment.展开更多
Current ever-accumulating plastic waste can be considered a significant carbon resource for energy conversion and chemical production.The development of new approaches for upcycling plastic waste through chemical degr...Current ever-accumulating plastic waste can be considered a significant carbon resource for energy conversion and chemical production.The development of new approaches for upcycling plastic waste through chemical degradation may enable circularity and promote closed-loop recycling of carbon sources compared to traditional recycling methods.Zeolite,a widely used solid acid catalyst with high industrial potential in petroleum and biomass refining,has been extensively studied for its role in transforming plastics.In this review,we present an overview of zeolite-based catalytic systems for the chemical recycling of plastic waste and discuss how zeolites could potentially contribute to the future development of a circular economy.To provide a comprehensive understanding,we begin with a brief introduction to zeolites,analyzing their key features and exploring their opportunities as well as challenges in processing plastic waste.Subsequently,we delve into the chemistry of catalytic cracking and tandem catalysis using zeolite-based catalysts on plastics.Overall,we emphasize the importance of intelligent catalyst design and lower-energy pathways to incentivize plastic upcycling while alleviating the burden caused by waste plastics.展开更多
The unprecedented growth of electric vehicles featuring lithium-ion batteries has led to a significant increase in the amount of waste generated,posing pressing waste management challenges for both industry professio ...The unprecedented growth of electric vehicles featuring lithium-ion batteries has led to a significant increase in the amount of waste generated,posing pressing waste management challenges for both industry professio nals and environmental regulators.To address these issues,conventio nal pyrometallurgical,hydrometallurgical,and direct recycling methods are commonly employed to promote sustainable battery development.However,these methods are often hindered by laborious purification processes and the generation of low-profit products such as Li_(2)CO_(3),CoSO_(4),NiSO_(4),etc.Herein,an upcycling technology involving a low-temperature solid-to-solid reaction and water leaching procedures is introduced to transform spent LiCoO_(2)cathode materials into value-added cobalt sulfide-based electrocatalysts.The regenerated electrocatalysts exhibit exceptional performance in the oxygen evolution reaction,surpassing that of the benchmark RuO_(2)catalyst.This proposed upcycling method provides researchers with an alternative way to convert the metallic components of waste lithium-ion batteries into high-value Co-,Ni-,Fe-,and Mn-based catalysts.展开更多
A notable retiring wave for lithium iron phosphate(LiFePO_(4),LFP)-based lithium-ion batteries(LIBs)is expected in the coming years,which urges the establishment of complete and eco-friendly recycling chains.Currently...A notable retiring wave for lithium iron phosphate(LiFePO_(4),LFP)-based lithium-ion batteries(LIBs)is expected in the coming years,which urges the establishment of complete and eco-friendly recycling chains.Currently,the industrial practice for these degraded LFP materials heavily relies on the hydrometallurgical strategies,which aim for the selective leaching of valuable Li element;this,however,leads to the accumulation of FePO_(4)by-product as a waste,which is neither economical nor sustainable.Considering the increasing demand on performance for next-generation LFP cathode materials,herein,we demonstrate a facile,green,and economic method to upcycle FePO_(4)residues from spent LIBs into high-performance LFP materials for direct reusages.The upcycling protocol involves simultaneous structural restoration of LFP lattices and hierarchical assembly of graphene-based conductive frameworks.As a result,the upcycled LFP cathode material delivers exceptional rate performance(discharge capacity of 125.6 mA h g^(-1)at 5 C or 93.6 mA h g^(-1)at 15 C)and cycling stability under high-rate conditions(capacity retention of 99.5%after 300 cycles at 1 C or 96.7%after 1000 cycles at 5 C).Moreover,the electrochemical performance is largely maintained at low temperatures.The upcycling strategy sheds light on the closed-loop development of LIB industry.展开更多
Environmental pollution and energy crisis are the most important problems all over the world.Polyethylene terephthalate(PET)is a widely used and difficult-to-degrade plastic that can be decomposed into terephthalic ac...Environmental pollution and energy crisis are the most important problems all over the world.Polyethylene terephthalate(PET)is a widely used and difficult-to-degrade plastic that can be decomposed into terephthalic acid(PTA)and ethylene glycol(EG),and the EG can be electrocatalytically oxidized to high-value-added formic acid(FA).However,the commercial RuO_(2)cannot support the EG oxidative reaction(EGOR)due to its strong absorption of intermediates and less exposed active sites,so the RuSb_(0.92)O_(1.76)medium-entropy alloy oxide(MEAO)was constructed in this work.The RuSb_(0.92)O_(1.76)fills up the O vacancy of RuO_(2)and repairs the instability of RuO_(2),and the lattice O in the RuSb_(0.92)O_(1.76)promotes the EGOR by sacrificing itself to generate O vacancies.The RuSb_(0.92)O_(1.76)shows a low EGOR potential of 1.13 V at 10 mA cm^(-2),and a low hydrogen evolution reaction(HER)potential of 43 m V at 10 mA cm^(-2).The RuSb_(0.92)O_(1.76)shows a high Faradic efficiency(FE)of close to 100%through the glycolaldehyde/GA pathway via the in situ ATR-IR spectroscopy.Density functional theory(DFT)reveals that RuSb_(0.92)O_(1.76)has a moderate adsorption capacity for intermediates in the EGOR.This work provides a potential avenue for the MEAO catalysts in electrocatalytic plastic upcycling coupling hydrogen energy.展开更多
Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are ...Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are restricted by the expensive monomer(1,4-cyclohexanedimethanol,CHDM).Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate(DMCD)can promote the production of CHDM in large scale.In this work,a bifunctional Ru/UiO-66_(def)-SO_(3)H catalyst was synthesized and utilized in coupled methanolysis(of waste PET to dimethyl terephthalate(DMT))and hydrogenation(of DMT to DMCD)under mild condition.Characterizations revealed that Ru/UiO-66_(def)-SO_(3)H possessed mesopores(dominant channels of 2.72 and 3.44 nm),enlarged surface area(998 m^(2)·g^(–1)),enhanced acidity(580μmol·g^(–1)),and Ru nanoparticles(NPs)dispersed highly(45.1%)compared to those of Ru/UiO-66.These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously,promoting the performance of direct upgrading of PET to DMCD in one pot.In particular,the conversion of PET and yield of DMCD over Ru/UiO-66_(def)-SO_(3)H reached 100%and 97.7%at 170℃and 3 MPa H_(2)within 6 h.Moreover,Ru/UiO-66_(def)-SO3H was also capable for the upcycling of waste PET-based products including beverage bottles,textile fiber and packaging film to DMCD.展开更多
Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should t...Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.展开更多
Of all the existing materials, plastics are no doubt among the most versatile ones. However, the extreme increases in plastic production as well as the difficulty of the material for degradation have led to a huge num...Of all the existing materials, plastics are no doubt among the most versatile ones. However, the extreme increases in plastic production as well as the difficulty of the material for degradation have led to a huge number of plastic wastes. Their recycling rate after disposal is less than 10%, resulting in a series of serious environmental and ecological problems as well as a significant waste of resources. Current recycling methods generally suffer from large energy consumption, the low utilization rate of recycled products with low added value, and produce other waste during the process. Here, we summarized recentlydeveloped chemical recycling ways on commodity plastics, especially new catalytic paths in production of fuels, high-valued chemicals and advanced materials from a single virgin or a mixture of plastic waste,which have emerged as promising ways to valorize waste plastics more economically and environmentally friendly. The new catalyst design criteria as well as innovative catalytic paths and technologies for plastic upcycling are highlighted. Beyond energy recovery by incineration, these approaches demonstrate how waste plastics can be a viable feedstock for energy use with the generation of clean H_(2), high-quality liquid fuels and materials for energy storage, and help inspiring more catalytic process on plastic upcycling to overcome the economical hurdle and building a circular plastic economy.展开更多
Electro-upcycling of plastic waste into value-added chemicals/fuels is an attractive and sustainable way for plastic waste management.Recently,electrocatalytically converting polyethylene terephthalate(PET)into format...Electro-upcycling of plastic waste into value-added chemicals/fuels is an attractive and sustainable way for plastic waste management.Recently,electrocatalytically converting polyethylene terephthalate(PET)into formate and hydrogen has aroused great interest,while developing low-cost catalysts with high efficiency and selectivity for the central ethylene glycol(PET monomer)oxidation reaction(EGOR)remains a challenge.Herein,a high-performance nickel sulfide catalyst for plastic waste electro-upcycling is designed by a cobalt and chloride co-doping strategy.Benefiting from the interconnected ultrathin nanosheet architecture,dual dopants induced upshifting d band centre and facilitated in situ structural reconstruction,the Co and Cl co-doped Ni_(3)S_(2)(Co,Cl-NiS)outperforms the singledoped and undoped analogues for EGOR.The self-evolved sulfide@oxyhydroxide heterostructure catalyzes EG-to-formate conversion with high Faradic efficiency(>92%)and selectivity(>91%)at high current densities(>400 mA cm^(−2)).Besides producing formate,the bifunctional Co,Cl-NiS-assisted PET hydrolysate electrolyzer can achieve a high hydrogen production rate of 50.26 mmol h^(−1)in 2 M KOH,at 1.7 V.This study not only demonstrates a dual-doping strategy to engineer cost-effective bifunctional catalysts for electrochemical conversion processes,but also provides a green and sustainable way for plastic waste upcycling and simultaneous energy-saving hydrogen production.展开更多
Direct recycling has been regarded as one of the most promising approaches to dealing with the increasing amount of spent lithium‐ion batteries(LIBs).However,the current direct recycling method remains insufficient t...Direct recycling has been regarded as one of the most promising approaches to dealing with the increasing amount of spent lithium‐ion batteries(LIBs).However,the current direct recycling method remains insufficient to regenerate outdated cathodes to meet current industry needs as it only aims at recovering the structure and composition of degraded cathodes.Herein,a nickel(Ni)and manganese(Mn)co‐doping strategy has been adopted to enhance LiCoO_(2)(LCO)cathode for next‐generation high‐performance LIBs through a conventional hydrothermal treatment combined with short annealing approach.Unlike direct recycling methods that make no changes to the chemical composition of cathodes,the unique upcycling process fabricates a series of cathodes doped with different contents of Ni and Mn.The regenerated LCO cathode with 5%doping delivers excellent electrochemical performance with a discharge capacity of 160.23 mAh g^(−1) at 1.0 C and capacity retention of 91.2%after 100 cycles,considerably surpassing those of the pristine one(124.05 mAh g^(−1) and 89.05%).All results indicate the feasibility of such Ni–Mn co‐doping‐enabled upcycling on regenerating LCO cathodes.展开更多
基金financially supported by the National Key Research and Development Program of China(2023YFB3809300)。
文摘With the approaching of large-scale retirement of power lithium-ion batteries(LIBs),their urgent handling is required for environmental protection and resource reutilization.However,at present,substantial spent power batteries,especially for those high recovery value cathode materials,have not been greenly,sustainably,and efficiently recycled.Compared to the traditional recovery method for cathode materials with high energy consumption and severe secondary pollution,the direct repair regeneration,as a new type of short-process and efficient treatment methods,has attracted widespread attention.However,it still faces challenges in homogenization repair,electrochemical performance decline,and scaling-up production.To promote the direct regeneration technology development of failed NCM materials,herein we deeply discuss the failure mechanism of nickel-cobalt-manganese(NCM)ternary cathode materials,including element loss,Li/Ni mixing,phase transformation,structural defects,oxygen release,and surface degradation and reconstruction.Based on this,the detailed analysis and summary of the direct regeneration method embracing solid-phase sintering,eutectic salt assistance,solvothermal synthesis,sol-gel process,spray drying,and redox mediation are provided.Further,the upcycling strategy for regeneration materials,such as single-crystallization and high-nickelization,structural regulation,ion doping,and surface engineering,are discussed in deep.Finally,the challenges faced by the direct regeneration and corresponding countermeasures are pointed out.Undoubtedly,this review provides valuable guidance for the efficient and high-value recovery of failed cathode materials.
基金financially supported by the National Key Research and Development Program of China(No.2023YFC3904800)the National Outstanding Young Scientists Fund(No.5a2125002)+7 种基金the National Science Foundation of China(No.22476073)the Key Project of Jiangxi Provincial Research and Development Program(Nos.20223BBG74006 and 20243BBI91001)the China Postdoctoral Science Foundation(No.2024M751282)the “Thousand Talents Program”of Jiangxi Province(S_(2)021GDQN2161)the Key Project of Ganzhou City Research and Development Program(No.2023PGX17350)the Science&Technology Talent Lifting Project of Hunan Province(No.2022TJ-N16)the Natural Science Foundation of Hunan Province China(No.2024JJ4022,2023JJ30277)the Open-End Fund for National-Local Joint Engineering Research Center of Heavy Metals Pollutants Control and Resource Utilization(ES_(2)02480184)。
文摘Lithium-ion batteries(LIBs)are critical for the rapid growth of electric vehicles(EVs),but their inherent lifespan leads to numerous retirements and resource challenges.The efficacy of conventional recycling techniques is increasingly compromised by their high energy consumption and secondary pollution,rendering them less responsive to greener and more sustainable requirement of rapid development.Thus,the direct recycling process emerged and was considered as a more expedient and convenient method of recycling compared to the conventional recycling modes that are currently in study.However,due to the reliance on the indispensable sintering process,direct recycling still faces considerable challenges,motivating researchers to explore faster,greener,and more cost-effective strategies for LIBs recycling,Inspiringly,Joule heating recycling(JHR),an emerging technique,offers rapid,efficient impurity removal and material regeneration with minimal environmental impact,addressing limitations of existing methods.This method reduces the time for direct recycling of spent LIBs by a factor of at least three orders of magnitude and exhibits significant potential for future industrial production.Unfortunately,due to the lack of systematic organization and reporting,this next generation approach to direct recycling of spent LIBs has not yet gained much interest.To facilitate a more profound comprehension of rising flash recycling strategy,in this study,JHR is distinguished into two distinctive implementation pathways(including flash Joule heating and carbon thermal shock),designed to accommodate varying pretreatment stages and diverse spent LIBs materials.Subsequently,the advantages of the recently developed JHR of spent LIBs in terms of material performance,environmental friendliness,and economic viability are discussed in detail.Ultimately,with the goal of achieving more attractive society effects,the future direction of JHR of spent LIBs and its potential for practical application are proposed and envisaged.
基金financially supported by the National Key R&D Program of China(2023YFA1506602 and 2021YFA1501102)the National Natural Science Foundation of China(21932002,22276023,22402019)+1 种基金the Fundamental Research Funds for the Central Universities(DUT22LAB602)Liaoning Binhai Laboratory Project(LBLF-202306)。
文摘Cold plasma-assisted catalytic upcycling of polyolefin wastes integrated with CO_(2)into value-added chemicals is a promising solution for mitigating the global carbon emissions and fossil energy crisis,but still challenging due to the complexity of products and low energy efficiency.Given this,a novel one-stage process of cold plasma coupled with Ga-modified hierarchical H-ZSM-5(Ga/Hie-ZSM-5)catalyst for polyolefins upgrading was designed with polyolefins followed by the catalysts within the plasma region,which facilitated the upcycling of polyolefins to light olefins and CO_(2)activation by plasma,and thereby the enhanced synergy between cold plasma and catalysts for aromatics production.At an input power of ca.45 W without external heating,the low-density polyethylene(LDPE)waste was completely converted with the assistance of CO_(2)and the yield of oil products over the Ga/Hie-ZSM-5 catalyst was highly up to 62.2 wt%,with nearly 100% selectivity of aromatics.Meanwhile,the degradation efficiency of LDPE and the energy efficiency could reach 2.5 g_(LDPE)·g_(cat)^(-1)·h^(-1)and 55.56 g_(LDPE)·g_(cat)^(-1)·kW^(-1)h^(-1),respectively.Mechanism investigation revealed that the plasma and CO_(2)synergistically affect the primary cracking of LDPE,forming a primary product enriched in olefins and a small amount of CO.Subsequently,the produced olefins intermediates were further aromatized via cyclizationdehydrogenation route on the Ga/Hie-ZSM-5 catalyst with assistance of CO_(2)under the synergistic effect of plasma-catalysis.This work offers a feasible strategy to improve the yield of aromatic products for the plasma-catalytic upcycling of polyolefins and CO_(2)at ambient pressure without any external heating.
基金supported by the National Natural Science Foundation of China(Nos.22125103 and 22301077)STCSM(22JC140100)Shanghai Pujiang Program(No.22PJ1403200)。
文摘Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and chemicals.However,studies on the depolymerization and functionalization of challenging super engineering plastics have remained in early stage and underexplored.In this review,we would like to discuss the representative accomplishments and mechanism insights on chemical protocols achieved in depolymerization of super engineering plastics,especially for poly(phenylene sulfide)(PPS),poly(aryl ether)s including poly(ether ether ketone)(PEEK),polysulfone(PSU),polyphenylsulfone(PPSU)and polyethersulfone(PES).We anticipate that this review will provide an overall perspective on the current status and future trends of this emerging field.
基金the Beijing Natural Science Foundation(Z240029)the National Natural Science Foundation of China(22472004)+2 种基金China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Researchthe New Cornerstone Science Foundationsupport from the Tencent Foundation through the Xplorer Prize.
文摘Polyvinyl chloride(PVC)is one of the most widely used plastic materials worldwide,particularly in long-life applications such as construction materials.However,recycling options for PVC waste remain limited,as conventional methods often degrade material quality or generate environmentally hazardous byproducts.In this study,we demonstrate an efficient process to convert PVC into new polymers with variable aromatic groups,using triethylsilane as the reductant in different solvents.This approach enables the production of polymers analogous to functionalized polyethylene(PE),which are typically challenging to obtain through conventional copolymerization or direct post-modification of C-H bonds in PE.The resulting polymers exhibit tunable thermal and mechanical properties depending on the introduced aromatic groups,which not only enhance the sustainable valorization of PVC waste,but also provide an opportunity for the synthesis of new functionalized polymers.
基金We highly thank the funding from the National Natural Science Foundation of China(grants 22222806,22178162,22072065,and 22408170)the Distinguished Youth Foundation of Jiangsu Province(BK20220053)+2 种基金the National Key Research and Development Program of China(2024YFE0206900)the Six Talent Peaks Project in Jiangsu Province(grant JNHB-035)Agency for Science,Technology and Research(A*STAR)through Low Carbon Energy Research Finding Initiative(LCERFI01-0033|U2102d2006).
文摘Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we constructed ultralow-coordinated Ni species with Ni–O coordination number of∼3 via a hydrothermal synthesis-sulfidation-annealing process and electrochemical activation and demonstrated the vital role in accelerating the proton deintercalation and reactive oxygen intermediate·OH formation during electro-reforming polyethylene terephthalate hydrolysate(POR).The target catalyst NiCoSx/NF afforded a high formate productivity of 7.4 mmol cm^(−2)h^(−1)at∼600 mA cm^(−2)with a formate Faradic efficiency(FE_(formate))of 92.4%in POR and maintained a FE_(formate)of∼90%for 100 h at 2 A in a membrane electrode assembly electrolyzer.Coupling POR on NiCoSx/NF with carbon dioxide reduction reaction on oxygen vacancies enriched Vo-BiSnO reached effective concurrent formate production with 172.7%of FE_(formate)at 500 mA cm^(−2)and long-term stability.Such excellent performance shows the great prospect of electrocatalyst design by regulating the local metal environment.
文摘Current ever-accumulating plastic waste can be considered a significant carbon resource for energy conversion and chemical production.The development of new approaches for upcycling plastic waste through chemical degradation may enable circularity and promote closed-loop recycling of carbon sources compared to traditional recycling methods.Zeolite,a widely used solid acid catalyst with high industrial potential in petroleum and biomass refining,has been extensively studied for its role in transforming plastics.In this review,we present an overview of zeolite-based catalytic systems for the chemical recycling of plastic waste and discuss how zeolites could potentially contribute to the future development of a circular economy.To provide a comprehensive understanding,we begin with a brief introduction to zeolites,analyzing their key features and exploring their opportunities as well as challenges in processing plastic waste.Subsequently,we delve into the chemistry of catalytic cracking and tandem catalysis using zeolite-based catalysts on plastics.Overall,we emphasize the importance of intelligent catalyst design and lower-energy pathways to incentivize plastic upcycling while alleviating the burden caused by waste plastics.
基金financial support from the National Natural Science Foundation of China(21702143,52303092)Talent Recruitment Project of Guangdong Province(No.2023QN10X078)+1 种基金Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(No.YPML-2023050278)Guangdong Basic and Applied Basic Research Foundation Special Projects——GuangdongShenzhen Joint Funds(2022A1515110027)。
文摘The unprecedented growth of electric vehicles featuring lithium-ion batteries has led to a significant increase in the amount of waste generated,posing pressing waste management challenges for both industry professio nals and environmental regulators.To address these issues,conventio nal pyrometallurgical,hydrometallurgical,and direct recycling methods are commonly employed to promote sustainable battery development.However,these methods are often hindered by laborious purification processes and the generation of low-profit products such as Li_(2)CO_(3),CoSO_(4),NiSO_(4),etc.Herein,an upcycling technology involving a low-temperature solid-to-solid reaction and water leaching procedures is introduced to transform spent LiCoO_(2)cathode materials into value-added cobalt sulfide-based electrocatalysts.The regenerated electrocatalysts exhibit exceptional performance in the oxygen evolution reaction,surpassing that of the benchmark RuO_(2)catalyst.This proposed upcycling method provides researchers with an alternative way to convert the metallic components of waste lithium-ion batteries into high-value Co-,Ni-,Fe-,and Mn-based catalysts.
基金supported by the National Natural Science Foundation of China(22375081 and U21A20500)the Jiangxi Provincial Natural Science Foundation(20212ACB204016)the support from Nanchang University。
文摘A notable retiring wave for lithium iron phosphate(LiFePO_(4),LFP)-based lithium-ion batteries(LIBs)is expected in the coming years,which urges the establishment of complete and eco-friendly recycling chains.Currently,the industrial practice for these degraded LFP materials heavily relies on the hydrometallurgical strategies,which aim for the selective leaching of valuable Li element;this,however,leads to the accumulation of FePO_(4)by-product as a waste,which is neither economical nor sustainable.Considering the increasing demand on performance for next-generation LFP cathode materials,herein,we demonstrate a facile,green,and economic method to upcycle FePO_(4)residues from spent LIBs into high-performance LFP materials for direct reusages.The upcycling protocol involves simultaneous structural restoration of LFP lattices and hierarchical assembly of graphene-based conductive frameworks.As a result,the upcycled LFP cathode material delivers exceptional rate performance(discharge capacity of 125.6 mA h g^(-1)at 5 C or 93.6 mA h g^(-1)at 15 C)and cycling stability under high-rate conditions(capacity retention of 99.5%after 300 cycles at 1 C or 96.7%after 1000 cycles at 5 C).Moreover,the electrochemical performance is largely maintained at low temperatures.The upcycling strategy sheds light on the closed-loop development of LIB industry.
基金supported by the National Natural Science Foundation of China(22302019)Changzhou Sci&Tech Program(CJ20220214)。
文摘Environmental pollution and energy crisis are the most important problems all over the world.Polyethylene terephthalate(PET)is a widely used and difficult-to-degrade plastic that can be decomposed into terephthalic acid(PTA)and ethylene glycol(EG),and the EG can be electrocatalytically oxidized to high-value-added formic acid(FA).However,the commercial RuO_(2)cannot support the EG oxidative reaction(EGOR)due to its strong absorption of intermediates and less exposed active sites,so the RuSb_(0.92)O_(1.76)medium-entropy alloy oxide(MEAO)was constructed in this work.The RuSb_(0.92)O_(1.76)fills up the O vacancy of RuO_(2)and repairs the instability of RuO_(2),and the lattice O in the RuSb_(0.92)O_(1.76)promotes the EGOR by sacrificing itself to generate O vacancies.The RuSb_(0.92)O_(1.76)shows a low EGOR potential of 1.13 V at 10 mA cm^(-2),and a low hydrogen evolution reaction(HER)potential of 43 m V at 10 mA cm^(-2).The RuSb_(0.92)O_(1.76)shows a high Faradic efficiency(FE)of close to 100%through the glycolaldehyde/GA pathway via the in situ ATR-IR spectroscopy.Density functional theory(DFT)reveals that RuSb_(0.92)O_(1.76)has a moderate adsorption capacity for intermediates in the EGOR.This work provides a potential avenue for the MEAO catalysts in electrocatalytic plastic upcycling coupling hydrogen energy.
文摘Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are restricted by the expensive monomer(1,4-cyclohexanedimethanol,CHDM).Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate(DMCD)can promote the production of CHDM in large scale.In this work,a bifunctional Ru/UiO-66_(def)-SO_(3)H catalyst was synthesized and utilized in coupled methanolysis(of waste PET to dimethyl terephthalate(DMT))and hydrogenation(of DMT to DMCD)under mild condition.Characterizations revealed that Ru/UiO-66_(def)-SO_(3)H possessed mesopores(dominant channels of 2.72 and 3.44 nm),enlarged surface area(998 m^(2)·g^(–1)),enhanced acidity(580μmol·g^(–1)),and Ru nanoparticles(NPs)dispersed highly(45.1%)compared to those of Ru/UiO-66.These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously,promoting the performance of direct upgrading of PET to DMCD in one pot.In particular,the conversion of PET and yield of DMCD over Ru/UiO-66_(def)-SO_(3)H reached 100%and 97.7%at 170℃and 3 MPa H_(2)within 6 h.Moreover,Ru/UiO-66_(def)-SO3H was also capable for the upcycling of waste PET-based products including beverage bottles,textile fiber and packaging film to DMCD.
基金financially supported by the National Natural Science Foundation of China(Nos.52373007 and 52073296)Innovative Leading Talent of Taihu Lake Talent Plan in Wuxi City+1 种基金Zhejiang Ten Thousand Talent ProgramResearch startup fund from Jiangnan University。
文摘Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.
基金supported by the National Key R&D Program of China (No. 2021YFA1501700)the Funding for Hundred Talent Program B of Sichuan University (20822041E4079)+2 种基金the Institutional Research Fund from Sichuan University (2020SCUNL205)the State Key Laboratory of Polymer Materials Engineering Open Fund project (sklpme2020-1-02)the Fundamental Research Funds for the Central Universities。
文摘Of all the existing materials, plastics are no doubt among the most versatile ones. However, the extreme increases in plastic production as well as the difficulty of the material for degradation have led to a huge number of plastic wastes. Their recycling rate after disposal is less than 10%, resulting in a series of serious environmental and ecological problems as well as a significant waste of resources. Current recycling methods generally suffer from large energy consumption, the low utilization rate of recycled products with low added value, and produce other waste during the process. Here, we summarized recentlydeveloped chemical recycling ways on commodity plastics, especially new catalytic paths in production of fuels, high-valued chemicals and advanced materials from a single virgin or a mixture of plastic waste,which have emerged as promising ways to valorize waste plastics more economically and environmentally friendly. The new catalyst design criteria as well as innovative catalytic paths and technologies for plastic upcycling are highlighted. Beyond energy recovery by incineration, these approaches demonstrate how waste plastics can be a viable feedstock for energy use with the generation of clean H_(2), high-quality liquid fuels and materials for energy storage, and help inspiring more catalytic process on plastic upcycling to overcome the economical hurdle and building a circular plastic economy.
基金supported by the Australian Research Council(ARC)Discovery Project(DP220101139)Dr.Wei Wei acknowledges the support of the Australian Research Council(ARC)through Project DE220100530.
文摘Electro-upcycling of plastic waste into value-added chemicals/fuels is an attractive and sustainable way for plastic waste management.Recently,electrocatalytically converting polyethylene terephthalate(PET)into formate and hydrogen has aroused great interest,while developing low-cost catalysts with high efficiency and selectivity for the central ethylene glycol(PET monomer)oxidation reaction(EGOR)remains a challenge.Herein,a high-performance nickel sulfide catalyst for plastic waste electro-upcycling is designed by a cobalt and chloride co-doping strategy.Benefiting from the interconnected ultrathin nanosheet architecture,dual dopants induced upshifting d band centre and facilitated in situ structural reconstruction,the Co and Cl co-doped Ni_(3)S_(2)(Co,Cl-NiS)outperforms the singledoped and undoped analogues for EGOR.The self-evolved sulfide@oxyhydroxide heterostructure catalyzes EG-to-formate conversion with high Faradic efficiency(>92%)and selectivity(>91%)at high current densities(>400 mA cm^(−2)).Besides producing formate,the bifunctional Co,Cl-NiS-assisted PET hydrolysate electrolyzer can achieve a high hydrogen production rate of 50.26 mmol h^(−1)in 2 M KOH,at 1.7 V.This study not only demonstrates a dual-doping strategy to engineer cost-effective bifunctional catalysts for electrochemical conversion processes,but also provides a green and sustainable way for plastic waste upcycling and simultaneous energy-saving hydrogen production.
基金support of NanoFAB in Electron Microscopy and FIB sample preparation at the University of Alberta in Canadasupported by the Natural Sciences and Engineering Research Council of Canada(NSERC)+3 种基金through the Discovery Grant Program(RGPIN-2018-06725)the Discovery Accelerator Supplement Grant program(RGPAS-2018-522651)by the New Frontiers in Research Fund-Exploration program(NFRFE-2019-00488)financial support from the University of Alberta and Future Energy Systems(FES-T06-Q03).
文摘Direct recycling has been regarded as one of the most promising approaches to dealing with the increasing amount of spent lithium‐ion batteries(LIBs).However,the current direct recycling method remains insufficient to regenerate outdated cathodes to meet current industry needs as it only aims at recovering the structure and composition of degraded cathodes.Herein,a nickel(Ni)and manganese(Mn)co‐doping strategy has been adopted to enhance LiCoO_(2)(LCO)cathode for next‐generation high‐performance LIBs through a conventional hydrothermal treatment combined with short annealing approach.Unlike direct recycling methods that make no changes to the chemical composition of cathodes,the unique upcycling process fabricates a series of cathodes doped with different contents of Ni and Mn.The regenerated LCO cathode with 5%doping delivers excellent electrochemical performance with a discharge capacity of 160.23 mAh g^(−1) at 1.0 C and capacity retention of 91.2%after 100 cycles,considerably surpassing those of the pristine one(124.05 mAh g^(−1) and 89.05%).All results indicate the feasibility of such Ni–Mn co‐doping‐enabled upcycling on regenerating LCO cathodes.
