As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,ag...As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.展开更多
Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. H...Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. Herein, by incorporating the cobalt-oxide bonds and polyaniline(PANI) with two-dimension zeolitic imidazolate frameworks(ZIFs), a novel bifunctional catalyst(Co-O-ZIF/PANI) for Zn-air battery was designed based on a facile and eco-friendly method. This Co-O-ZIF/PANI with optimized surface adsorption effect and suitable Co^(3+)/Co^(2+)ratio, exhibits eminent electrocatalytic activity toward both oxygen reduction and evolution reaction. The as-assembled liquid ZABs based on Co-O-ZIF/PANI achieves a remarkable maximum power density of 123.1 m W cm^(-2) and low discharge-charge voltage gap of 0.81 V at 5 m A cm^(-2) for over 300 cycles. Operando Raman spectroscopy reveals that the excellent performance origins from the optimized surface chemisorption property of O_(2) and H_(2)O brought by Co–O bonds and PANI. This work provides a novel prospect to develop efficient MOF derived bifunctional electrocatalysts by optimizing surface chemisorption properties.展开更多
K-ion batteries(KIBs)have attracted tremendous attention and seen significant development because of their low price,high operating voltage,and properties similar to those of Li-ion batteries.In the field of developme...K-ion batteries(KIBs)have attracted tremendous attention and seen significant development because of their low price,high operating voltage,and properties similar to those of Li-ion batteries.In the field of development of full batteries,exploring high-performing and low-cost anode materials for K-ion storage is a crucial challenge.Owing to their excellent cost effectiveness,abundant precursors,and environmental benignancy,hard carbons(HCs)are considered promising anode materials for KIBs.As a result,researchers have devoted much effort to quantify the properties and to understand the underlying mechanisms of HC-based anodes.In this review,we mainly introduce the electrochemical reaction mechanism of HCs in KIBs,and summarize approaches to further improve the electrochemical performance in HC-based materials for K-ion storage.In addition,we also highlight some advanced in situ characterization methods for understanding the evolutionary process underlying the potassiation–depotassiation process,which is essential for the directional electrochemical performance optimization of KIBs.Finally,we raise some challenges in developing smart-structured HC anode materials for KIBs,and propose rational design principles and perspectives serving as the guidance for the targeted optimization of HC-based KIBs.展开更多
基金the financial support from the National Natural Science Foundation of China(U1810111,51872124 and21676116)Natural Science Foundation of Guangdong Province,China(2018B030311010)+1 种基金the Fundamental Research Funds for the Central Universities(21617431)Key Laboratory of Biomass Chemical Engineering of Ministry of Education,Zhejiang University(2018BCE002)
文摘As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.
基金financially supported by the National Natural Science Foundation of China (51772135 and 51872124)the Ministry of Education of China (6141A02022516)+6 种基金the Natural Science Foundation of Guangdong Province (2014A030306010)the Natural Science Foundation of Guangdong Province (2021A1515010504)the Natural Science Key Foundation of Guangdong Province (2019B1515120056)the Natural Science Foundation of Guangzhou (201904010049)the Jinan University (88016105)the Innovation Team Project of Foshan City (FS0AA-KJ919-4402-0086)the Fundamental Research Foundation for the Central Universities(21617326 and 11619103)。
文摘Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. Herein, by incorporating the cobalt-oxide bonds and polyaniline(PANI) with two-dimension zeolitic imidazolate frameworks(ZIFs), a novel bifunctional catalyst(Co-O-ZIF/PANI) for Zn-air battery was designed based on a facile and eco-friendly method. This Co-O-ZIF/PANI with optimized surface adsorption effect and suitable Co^(3+)/Co^(2+)ratio, exhibits eminent electrocatalytic activity toward both oxygen reduction and evolution reaction. The as-assembled liquid ZABs based on Co-O-ZIF/PANI achieves a remarkable maximum power density of 123.1 m W cm^(-2) and low discharge-charge voltage gap of 0.81 V at 5 m A cm^(-2) for over 300 cycles. Operando Raman spectroscopy reveals that the excellent performance origins from the optimized surface chemisorption property of O_(2) and H_(2)O brought by Co–O bonds and PANI. This work provides a novel prospect to develop efficient MOF derived bifunctional electrocatalysts by optimizing surface chemisorption properties.
基金Fundamental Research Funds for the Central Universities,Grant/Award Numbers:21617330,21621406National Natural Science Foundation of China,Grant/Award Numbers:51702056,51772135,52172202+2 种基金Natural Science Foundation of Guangdong Province,Grant/Award Number:2021A1515010504Science and Technology Program of Guangzhou,Grant/Award Numbers:201605030008,202102020737Shenzhen Science and Technology Program,Grant/Award Number:JCYJ20200109113606007。
文摘K-ion batteries(KIBs)have attracted tremendous attention and seen significant development because of their low price,high operating voltage,and properties similar to those of Li-ion batteries.In the field of development of full batteries,exploring high-performing and low-cost anode materials for K-ion storage is a crucial challenge.Owing to their excellent cost effectiveness,abundant precursors,and environmental benignancy,hard carbons(HCs)are considered promising anode materials for KIBs.As a result,researchers have devoted much effort to quantify the properties and to understand the underlying mechanisms of HC-based anodes.In this review,we mainly introduce the electrochemical reaction mechanism of HCs in KIBs,and summarize approaches to further improve the electrochemical performance in HC-based materials for K-ion storage.In addition,we also highlight some advanced in situ characterization methods for understanding the evolutionary process underlying the potassiation–depotassiation process,which is essential for the directional electrochemical performance optimization of KIBs.Finally,we raise some challenges in developing smart-structured HC anode materials for KIBs,and propose rational design principles and perspectives serving as the guidance for the targeted optimization of HC-based KIBs.