Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability...Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.展开更多
Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-p...Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens.However,commercial EFAMEs,even with the highest epoxy value(ca.5.5-5.8%)so far,still suffer from fast leaching from the PVC matrix,burdening the environment and shortening lifespan of the artificial material.Here,we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester.Despite a low epoxy value(3.0%),the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value(5.8%).Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance,the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates,thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.展开更多
Plasticizer migration is responsible for premature coating failure in polyvinyl chloride(PVC)synthetic materials that continue to benefit our daily life as a reliable and cost-efficient simulant of genuine leather.In ...Plasticizer migration is responsible for premature coating failure in polyvinyl chloride(PVC)synthetic materials that continue to benefit our daily life as a reliable and cost-efficient simulant of genuine leather.In this context,the establishment of standard assays that measure the migration rate of plasticizers under varying scenarios plays a pivotal role in comparing durability of those PVC-derived leather-simulants.In this review,multiple methodologies developed over the last decade for determining plasticizer migration from PVC coating are compiled,with their operational principles,merits,and limitations being taken into consideration along with specific apparatus required for each.A concluding section discusses current challenges in this field,and highlights how nuclear magnetic resonance and computational simulation surpass conventional assays in yielding intercomparable results,and hence screening migration-resistant plasticizers in a labor-and time-saving way.Since migration resistance represents a decisive performance indicator of plasticizers,this systematic review may provide guidance to quite a few practitioners in PVC synthetic material industry,who are now engaged in validating various sustainable alternatives with performance allegedly equal to conventional but toxic di-(2-ethylhexyl)phthalate plasticizer.展开更多
基金supported by the National Natural Science Foundation of China(No.22108043)Natural Science Foundation of Guangdong Province,China(No.2023A1515012711).
文摘Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.
基金financial support of this work by National Key Research and Development Program of China(2017YFB0308600)National Natural Science Foundation of China(21878196)Fundamental Research Funds for the Central Universities,China(20826041C4159).
文摘Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens.However,commercial EFAMEs,even with the highest epoxy value(ca.5.5-5.8%)so far,still suffer from fast leaching from the PVC matrix,burdening the environment and shortening lifespan of the artificial material.Here,we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester.Despite a low epoxy value(3.0%),the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value(5.8%).Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance,the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates,thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.
基金Engineering Innovation Team Project of Sichuan University(2020SCUNG122)the Opening Project of Key Laboratory of Leather Chemistry and Engineering of Ministry of Education,Sichuan University(SCU2021D005).
文摘Plasticizer migration is responsible for premature coating failure in polyvinyl chloride(PVC)synthetic materials that continue to benefit our daily life as a reliable and cost-efficient simulant of genuine leather.In this context,the establishment of standard assays that measure the migration rate of plasticizers under varying scenarios plays a pivotal role in comparing durability of those PVC-derived leather-simulants.In this review,multiple methodologies developed over the last decade for determining plasticizer migration from PVC coating are compiled,with their operational principles,merits,and limitations being taken into consideration along with specific apparatus required for each.A concluding section discusses current challenges in this field,and highlights how nuclear magnetic resonance and computational simulation surpass conventional assays in yielding intercomparable results,and hence screening migration-resistant plasticizers in a labor-and time-saving way.Since migration resistance represents a decisive performance indicator of plasticizers,this systematic review may provide guidance to quite a few practitioners in PVC synthetic material industry,who are now engaged in validating various sustainable alternatives with performance allegedly equal to conventional but toxic di-(2-ethylhexyl)phthalate plasticizer.