甘油是生物质精炼的主要副产物(约占10%),年过剩量与低利用率导致其市场价格(0.24-0.6 US kg^(-1))较低.甘油是具有三个活性羟基的多元醇,被认为是生产高价值产品的理想原料.甲酸作为甘油转化最重要的产品之一,广泛应用于农药、皮革、...甘油是生物质精炼的主要副产物(约占10%),年过剩量与低利用率导致其市场价格(0.24-0.6 US kg^(-1))较低.甘油是具有三个活性羟基的多元醇,被认为是生产高价值产品的理想原料.甲酸作为甘油转化最重要的产品之一,广泛应用于农药、皮革、染料和医药行业,将甘油电氧化(EGOR)为甲酸(FA)不仅能有效避免资源过剩造成浪费,而且能满足未来对甲酸燃料电池的需求.然而甘油电催化氧化途径较为复杂,涉及反应中间产物的脱氢、吸附/解吸和C-C键裂解.本文将密度泛函理论(DFT)与实验相结合,研究了在精细构建的NiCo_(2)O_(4)纳米片上通过EGOR生产FA的反应机制.DFT计算结果表明,活性羟基(OH^(*))物种可以改变EGOR生产FA过程的决速步骤(RDS),通过调节吸附中间体的吸附能可获得理想的FA产率.其中,高度羟基化的NiCo_(2)O_(4)纳米片(311)-OH^(*)晶面上具有最低的吉布斯自由能,能显著提升反应过程动力学.在理论分析的基础上,通过简易的电沉积方法精准制备了超薄NiCo_(2)O_(4)纳米片(~1.7 nm),并采用X射线吸收精细结构谱和高分辨透射电镜对催化剂进行了结构分析.结果表明,NiCo_(2)O_(4)纳米片中四面体(A_(Td))和八面体(B_(Oh))配位具有内角共享的A_(Td)-O-B_(Oh)和边共享的B_(Oh)-O-B_(Oh)构型,金属间的协同作用有效改善了材料的电子效应,有利于提供更多的吸附位点并促进EGOR过程中的电荷转移.NiCo_(2)O_(4)纳米片在EGOR中的电荷转移电阻仅为0.94Ω,电化学活性表面积高达10.25 cm^(2).相比较电催化析氧反应,NiCo_(2)O_(4)纳米片表现出了较好的EGOR性能,在10 mA cm^(-2)的电流密度下阳极功耗降低了320 mV,在100 mA cm^(-2)的电流密度时的阳极电势仅为1.46 VRHE.此外,在120 h的稳定性测试中,甘油的转化率和FA的选择性可分别保持在89%和70%.多电位步骤实验、原位电化学阻抗谱和电子顺磁共振谱结果表明,NiCo_(2)O_(4)纳米片上原位产生的OH^(*)物种是EGOR过程中的直接活性中心,有利于将RDS从甘油酸脱氢裂解转化为甘油醛的脱氢步骤,并进一步促进C-C键的裂解.进一步结合理论预测,证实了OH^(*)物种是EGOR过程中的直接活性中心.综上,采用绿色高效的电催化手段促进甘油生产高附加值化学品是生物质链升级的重要举措,有效避免了传统的高温高压,以水为介质,原位利用OH^(*).本文为新型催化剂的未来设计和理解生物质基原料电氧化升级反应机制提供了新思路.展开更多
Iron oxide(Fe_(2)O_(3))emerges as a highly attractive anode candidate among rapidly expanding energy storage market.Nonethe-less,its considerable volume changes during cycling as an electrode material result in a vast...Iron oxide(Fe_(2)O_(3))emerges as a highly attractive anode candidate among rapidly expanding energy storage market.Nonethe-less,its considerable volume changes during cycling as an electrode material result in a vast reduced battery cycle life.In this work,an ap-proach is pioneered for preparing high-performance Fe_(2)O_(3)anode materials,by innovatively synthesizing a triple-layer yolk-shell Fe_(2)O_(3)uniformly coated with a conductive polypyrrole(Ppy)layer(Fe_(2)O_(3)@Ppy-TLY).The uniform polypyrrole coating introduces more reac-tion sites and adsorption sites,and maintains structure stability through charge-discharge process.In the uses as lithium-ion battery elec-trodes,Fe_(2)O_(3)@Ppy-TLY demonstrates high reversible specific capacity(maintaining a discharge capacity of 1375.11 mAh·g^(−1)after 500 cycles at 1 C),exceptional cycling stability(retaining the steady charge-discharge performance at 544.33 mAh·g^(−1)after 6000 ultrafast charge-discharge cycles at a 10 C current density),and outstanding high current charge-discharge performance(retaining a reversible ca-pacity of 156.75 mAh·g^(−1)after 10000 cycles at 15 C),thereby exhibiting superior lithium storage performance.This work introduces in-novative advancements for Fe_(2)O_(3)anode design,aiming to enhance its performance in energy storage fields.展开更多
Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in...Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.展开更多
Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile...Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.展开更多
Supercapacitors known as typical electrochemical capacitors have been considered as one of the most promising candidates of energy storage systems owing to their advantages such as high-power density,long life span an...Supercapacitors known as typical electrochemical capacitors have been considered as one of the most promising candidates of energy storage systems owing to their advantages such as high-power density,long life span and lower production cost.The electrode materials play a crucial role on properties of supercapacitors.Hence,many researches have been focused on the development of novel electrode materials for high-performance supercapacitors.NiCo_2O_4as supercapacitor electrode material has drawn more and more attentions in recent years due to its outstanding advantages,such as high theoretical capacity,low cost,natural abundance and easy of synthesis.However,the NiCo_2O_4always suffer from severe capacity deterioration because of the low electrical conductivity and small surface area.Hence,it is necessary to systematically and comprehensively summarize the progress in understanding and modifying NiCo_2O_4-based materials from various aspects.In this review,the structure and synthesis method of NiCo_2O_4-based materials are discussed in detail.And then,the major goal of this review is to highlight new progress in using proposed strategies to improve the cycling stability and rate capacity of NiCo_2O_4-based materials,including synthesis,control of special morphologies and design of composite materials.Finally,an insight into the future research and development of Ni Co_2O_4-based materials for supercapacitors is prospected.展开更多
La-doped Li2Mo0.9La0.2O4 was synthesized as an active anode material via the sol-gel process. The structural and morphological characteristics of the target product and the precursor were analyzed by XRD, SEM, and TG-...La-doped Li2Mo0.9La0.2O4 was synthesized as an active anode material via the sol-gel process. The structural and morphological characteristics of the target product and the precursor were analyzed by XRD, SEM, and TG-DTA. Crystal started to format at 300℃ and the optimum crystal structure was obtained at 700℃. By detecting battery performance, the charged and discharged platform was over 3.6 V; the anode exhibited a discharge capacity decay of 2% from its initial capacity （165 mA·h/g） after 20 cycles. Therefore, it was a perfect anode material.展开更多
文摘甘油是生物质精炼的主要副产物(约占10%),年过剩量与低利用率导致其市场价格(0.24-0.6 US kg^(-1))较低.甘油是具有三个活性羟基的多元醇,被认为是生产高价值产品的理想原料.甲酸作为甘油转化最重要的产品之一,广泛应用于农药、皮革、染料和医药行业,将甘油电氧化(EGOR)为甲酸(FA)不仅能有效避免资源过剩造成浪费,而且能满足未来对甲酸燃料电池的需求.然而甘油电催化氧化途径较为复杂,涉及反应中间产物的脱氢、吸附/解吸和C-C键裂解.本文将密度泛函理论(DFT)与实验相结合,研究了在精细构建的NiCo_(2)O_(4)纳米片上通过EGOR生产FA的反应机制.DFT计算结果表明,活性羟基(OH^(*))物种可以改变EGOR生产FA过程的决速步骤(RDS),通过调节吸附中间体的吸附能可获得理想的FA产率.其中,高度羟基化的NiCo_(2)O_(4)纳米片(311)-OH^(*)晶面上具有最低的吉布斯自由能,能显著提升反应过程动力学.在理论分析的基础上,通过简易的电沉积方法精准制备了超薄NiCo_(2)O_(4)纳米片(~1.7 nm),并采用X射线吸收精细结构谱和高分辨透射电镜对催化剂进行了结构分析.结果表明,NiCo_(2)O_(4)纳米片中四面体(A_(Td))和八面体(B_(Oh))配位具有内角共享的A_(Td)-O-B_(Oh)和边共享的B_(Oh)-O-B_(Oh)构型,金属间的协同作用有效改善了材料的电子效应,有利于提供更多的吸附位点并促进EGOR过程中的电荷转移.NiCo_(2)O_(4)纳米片在EGOR中的电荷转移电阻仅为0.94Ω,电化学活性表面积高达10.25 cm^(2).相比较电催化析氧反应,NiCo_(2)O_(4)纳米片表现出了较好的EGOR性能,在10 mA cm^(-2)的电流密度下阳极功耗降低了320 mV,在100 mA cm^(-2)的电流密度时的阳极电势仅为1.46 VRHE.此外,在120 h的稳定性测试中,甘油的转化率和FA的选择性可分别保持在89%和70%.多电位步骤实验、原位电化学阻抗谱和电子顺磁共振谱结果表明,NiCo_(2)O_(4)纳米片上原位产生的OH^(*)物种是EGOR过程中的直接活性中心,有利于将RDS从甘油酸脱氢裂解转化为甘油醛的脱氢步骤,并进一步促进C-C键的裂解.进一步结合理论预测,证实了OH^(*)物种是EGOR过程中的直接活性中心.综上,采用绿色高效的电催化手段促进甘油生产高附加值化学品是生物质链升级的重要举措,有效避免了传统的高温高压,以水为介质,原位利用OH^(*).本文为新型催化剂的未来设计和理解生物质基原料电氧化升级反应机制提供了新思路.
基金supported by the Natural Science Foundation of Jiangsu Province of China(No.BK20201008).
文摘Iron oxide(Fe_(2)O_(3))emerges as a highly attractive anode candidate among rapidly expanding energy storage market.Nonethe-less,its considerable volume changes during cycling as an electrode material result in a vast reduced battery cycle life.In this work,an ap-proach is pioneered for preparing high-performance Fe_(2)O_(3)anode materials,by innovatively synthesizing a triple-layer yolk-shell Fe_(2)O_(3)uniformly coated with a conductive polypyrrole(Ppy)layer(Fe_(2)O_(3)@Ppy-TLY).The uniform polypyrrole coating introduces more reac-tion sites and adsorption sites,and maintains structure stability through charge-discharge process.In the uses as lithium-ion battery elec-trodes,Fe_(2)O_(3)@Ppy-TLY demonstrates high reversible specific capacity(maintaining a discharge capacity of 1375.11 mAh·g^(−1)after 500 cycles at 1 C),exceptional cycling stability(retaining the steady charge-discharge performance at 544.33 mAh·g^(−1)after 6000 ultrafast charge-discharge cycles at a 10 C current density),and outstanding high current charge-discharge performance(retaining a reversible ca-pacity of 156.75 mAh·g^(−1)after 10000 cycles at 15 C),thereby exhibiting superior lithium storage performance.This work introduces in-novative advancements for Fe_(2)O_(3)anode design,aiming to enhance its performance in energy storage fields.
基金supported by the National Natural Science Foundation of China (52307239,52102300,52207234)the Natural Science Foundation of Hubei Province (2022CFB1003,2021CFA025)。
文摘Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.
基金financially supported by the National Natural Science Foundation of China(No.22072069)the Key Laboratory of Hubei Province for Coal Conversion and New Carbon Materials(Wuhan University of Science and Technology No.WKDM202303).
文摘Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.
基金financially supported by the National Natural Science Foundation of China (nos. 51774002 and 51672156)Anhui Provincial Science Fund for Excellent Young Scholars (no. gxyqZD2016066)+2 种基金the National Key Basic Research Program of China (2014CB932400)Guangdong special support program (2015TQ01N401)Shenzhen Technical Plan Project (KQJSCX20160226191136)
文摘Supercapacitors known as typical electrochemical capacitors have been considered as one of the most promising candidates of energy storage systems owing to their advantages such as high-power density,long life span and lower production cost.The electrode materials play a crucial role on properties of supercapacitors.Hence,many researches have been focused on the development of novel electrode materials for high-performance supercapacitors.NiCo_2O_4as supercapacitor electrode material has drawn more and more attentions in recent years due to its outstanding advantages,such as high theoretical capacity,low cost,natural abundance and easy of synthesis.However,the NiCo_2O_4always suffer from severe capacity deterioration because of the low electrical conductivity and small surface area.Hence,it is necessary to systematically and comprehensively summarize the progress in understanding and modifying NiCo_2O_4-based materials from various aspects.In this review,the structure and synthesis method of NiCo_2O_4-based materials are discussed in detail.And then,the major goal of this review is to highlight new progress in using proposed strategies to improve the cycling stability and rate capacity of NiCo_2O_4-based materials,including synthesis,control of special morphologies and design of composite materials.Finally,an insight into the future research and development of Ni Co_2O_4-based materials for supercapacitors is prospected.
文摘La-doped Li2Mo0.9La0.2O4 was synthesized as an active anode material via the sol-gel process. The structural and morphological characteristics of the target product and the precursor were analyzed by XRD, SEM, and TG-DTA. Crystal started to format at 300℃ and the optimum crystal structure was obtained at 700℃. By detecting battery performance, the charged and discharged platform was over 3.6 V; the anode exhibited a discharge capacity decay of 2% from its initial capacity （165 mA·h/g） after 20 cycles. Therefore, it was a perfect anode material.
