Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performanc...Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.展开更多
Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic pr...Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic properties. In order to simultaneously solve these problems, Pd/Co_(3)O_(4)–N–C multidimensional materials with porous structures is designed as the ORR catalysts. In details, the ZIF-67 with polyhedral structure was firstly synthesized and then annealed at high-temperature to prepare the N-doped Co_(3)O_(4)carbon-based material, which was used to homogeneously confine Pd nanoparticles and obtained the Pd/Co_(3)O_(4)–N–C series catalysts. The formation of Co–N and C–N bond could provide efficient active sites for ORR. Simultaneously, the strong electronic interaction in the interface between the Pd and N-doped Co_(3)O_(4)could disperse and avoid the agglomeration of Pd nanoparticles and ensure the exposure of active sites, which is crucial to lower the energy barrier toward ORR and substantially enhance the ORR kinetics. Hence, the Pd/Co_(3)O_(4)–N–C nanocompounds exhibited excellent ORR catalytic performance, ideal Pd mass activity, and durability in 0.1 mol L-1KOH solution compared with Co_(3)O_(4)–N–C and Pd/C. The scalable synthesis method, relatively low cost, and excellent electrochemical ORR performance indicated that the obtained Pd/Co_(3)O_(4)–N–C electrocatalyst had the potential for application on fuel cells.展开更多
A series of Pd/Co_3O_4 catalysts were prepared by Self-Propagating High-Temperature Synthesis(SHS)method in this study, and electric field was applied for catalytic combustion of lean methane over Pd/Co_3O_4 catalysts...A series of Pd/Co_3O_4 catalysts were prepared by Self-Propagating High-Temperature Synthesis(SHS)method in this study, and electric field was applied for catalytic combustion of lean methane over Pd/Co_3O_4 catalysts at low temperature. When electric field was applied, the catalytic combustion performance of Pd/Co_3O_4 catalysts was greatly improved, and the application of electric field could reduce the load of active element Pd to some extent while maintaining the same efficiency. Based on experimental tests and the analysis results of X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), H2-temperature-programmed reduction(H2-TPR) and in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS), the mechanism of catalytic oxidation of CH_4 over Pd/Co_3O_4 catalysts in electric field was proposed. The catalytic combustion of CH_4 occurs only when the temperature is higher than 250?C normally, but when electric field was applied, the whole process of CH_4 oxidation was promoted significantly and the reaction temperature was reduced. Electric field could promote the reduction of the support Co_3O_4 to release the lattice oxygen, resulting in the increase of PdOxand the surface chemisorbed oxygen, which could provide more active sites for the low-temperature oxidation of CH_4. Furthermore, electric field could accelerate the dehydroxylation of CoOOH to further enhance the activity of the catalysts.展开更多
亚胺型共价有机框架(COFs)材料多用于膜分离技术、气体储存和分离等,然而由于其较差的导电性和较低的物理化学稳定性少有应用于电催化析氢中。为了得到高稳定性且高活性的电催化剂,采用更为简便的溶剂热法合成了亚胺型COFs材料(TAPA-TFB...亚胺型共价有机框架(COFs)材料多用于膜分离技术、气体储存和分离等,然而由于其较差的导电性和较低的物理化学稳定性少有应用于电催化析氢中。为了得到高稳定性且高活性的电催化剂,采用更为简便的溶剂热法合成了亚胺型COFs材料(TAPA-TFB-COF),再以Co(OAC)_(2)·4H_(2)O为Co源,通过高温热解得到了二维片层自组装为3D微球结构的Co_(3)O_(4)复合氮掺杂碳材料(Co_(3)O_(4)/NC)。研究表明,由于3D微球结构、高温热解促进材料石墨化以及Co与杂原子N的协同作用,Co_(3)O_(4)/NC展现了优异的电催化析氢活性,起始电位从-0.92 V (vs.RHE)降到了-0.27 V (vs.RHE),电流密度提升为TAPA-TFB-COF的14倍,Tafel斜率仅为151 mV·dec^(-1),电化学反应电荷转移电阻(R_(ct))小至80.8Ω。展开更多
Enhancement of supercapacitors(SCs)with high-energy density and high-power density is still a great challenge.In this paper,a facile strategy for in situ anchoring of Co_(3)O_(4) particles on N doped carbon cloth(pCoN...Enhancement of supercapacitors(SCs)with high-energy density and high-power density is still a great challenge.In this paper,a facile strategy for in situ anchoring of Co_(3)O_(4) particles on N doped carbon cloth(pCoNCC)is reported.Due to the interaction of the doped N and Co_(3)O_(4),the electrochemical performance improves significantly,reaching 1,940.13 mF·cm^(−2) at 1 mA·cm^(−2) and energy density of 172.46μWh·cm^(−2) at the power density of 400μW·cm^(−2),much larger than that without N doping electrode of 28.5 mF·cm^(−2).An aqueous symmetric supercapacitor(ASSC)assembled by two pCoNCC electrodes achieves a maximum energy density of 447.42μWh·cm^(−2) and a highest power density of 8,000μW·cm^(−2).Utilizing such a high-energy storage ASSC,a digital watch and a temperature-humidity detector are powered for nearly 1 and 2 h,respectively.Moreover,the ASSC displays a superb electrochemical stability of 87.7%retention after 10,000 cycles at 40 mA·cm^(−2).This work would provide a new sight to enhance active materials performance and be beneficial for the future energy storage and supply systems.展开更多
Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short ...Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns. In this work, atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride （g-C3N4） using atomic layer deposition. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy （HAADF-STEM） confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle （NP） formation. During selective hydrogenation of acetylene in excess ethylene, the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/Al2O3 and Pd/SiO2 catalysts. In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement. More impressively, the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance. Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.展开更多
The preparation of highly active electrocatalysts with good durability and low cost for fuel cells is highly desir- able but still remains a significant challenge. Here we synthesized two dimensional （2D） C3N4 nanos...The preparation of highly active electrocatalysts with good durability and low cost for fuel cells is highly desir- able but still remains a significant challenge. Here we synthesized two dimensional （2D） C3N4 nanosheets supported palladium composites （C3N4/Pd） via a simple and convenient sonochemical approach. We have systematically stud- ied the electrocatalytic performance of as-prepared catalysts. We found that the prepared C3N4/Pd composites pos- sessed excellent catalytic activity and stability for oxygen reduction reaction （ORR） in alkaline media. Encourag- ingly, the C3N4/Pd catalysts exhibit the excellent electrocatalytic activity for methanol oxidation reaction （MOR） in alkaline media, even better than that of the commercial Pt/C catalyst, The excellent electrocatalytic performance of the 2D C3N4 nanosheets supported palladium composites catalysts results from their synergy effect between the ul- trathin substrate material with large surface area and excellent dispersion of palladium nanoparticles. This study demonstrates that sonochemical method opens up a new avenue for the preparation of electrocatalysts for fuel cells. We expect these materials are likely to find uses in a broad range of applications, for example, fuel cells, solar cells, batteries and other electrochemical analysis.展开更多
文摘Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.
基金funded by National Natural Science Foundation of China (21975129)Natural Science Foundation of Jiangsu Province (BK20190759)+1 种基金Nanjing Forestry UniversityPostgraduate Research & Practice Innovation Program of Jiangsu Province (SJCX21_0337)。
文摘Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic properties. In order to simultaneously solve these problems, Pd/Co_(3)O_(4)–N–C multidimensional materials with porous structures is designed as the ORR catalysts. In details, the ZIF-67 with polyhedral structure was firstly synthesized and then annealed at high-temperature to prepare the N-doped Co_(3)O_(4)carbon-based material, which was used to homogeneously confine Pd nanoparticles and obtained the Pd/Co_(3)O_(4)–N–C series catalysts. The formation of Co–N and C–N bond could provide efficient active sites for ORR. Simultaneously, the strong electronic interaction in the interface between the Pd and N-doped Co_(3)O_(4)could disperse and avoid the agglomeration of Pd nanoparticles and ensure the exposure of active sites, which is crucial to lower the energy barrier toward ORR and substantially enhance the ORR kinetics. Hence, the Pd/Co_(3)O_(4)–N–C nanocompounds exhibited excellent ORR catalytic performance, ideal Pd mass activity, and durability in 0.1 mol L-1KOH solution compared with Co_(3)O_(4)–N–C and Pd/C. The scalable synthesis method, relatively low cost, and excellent electrochemical ORR performance indicated that the obtained Pd/Co_(3)O_(4)–N–C electrocatalyst had the potential for application on fuel cells.
基金the National Key R&D Program of China(No.2016YFC0208000)the National Natural Science Foundation of China(No.51676127)
文摘A series of Pd/Co_3O_4 catalysts were prepared by Self-Propagating High-Temperature Synthesis(SHS)method in this study, and electric field was applied for catalytic combustion of lean methane over Pd/Co_3O_4 catalysts at low temperature. When electric field was applied, the catalytic combustion performance of Pd/Co_3O_4 catalysts was greatly improved, and the application of electric field could reduce the load of active element Pd to some extent while maintaining the same efficiency. Based on experimental tests and the analysis results of X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), H2-temperature-programmed reduction(H2-TPR) and in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS), the mechanism of catalytic oxidation of CH_4 over Pd/Co_3O_4 catalysts in electric field was proposed. The catalytic combustion of CH_4 occurs only when the temperature is higher than 250?C normally, but when electric field was applied, the whole process of CH_4 oxidation was promoted significantly and the reaction temperature was reduced. Electric field could promote the reduction of the support Co_3O_4 to release the lattice oxygen, resulting in the increase of PdOxand the surface chemisorbed oxygen, which could provide more active sites for the low-temperature oxidation of CH_4. Furthermore, electric field could accelerate the dehydroxylation of CoOOH to further enhance the activity of the catalysts.
文摘亚胺型共价有机框架(COFs)材料多用于膜分离技术、气体储存和分离等,然而由于其较差的导电性和较低的物理化学稳定性少有应用于电催化析氢中。为了得到高稳定性且高活性的电催化剂,采用更为简便的溶剂热法合成了亚胺型COFs材料(TAPA-TFB-COF),再以Co(OAC)_(2)·4H_(2)O为Co源,通过高温热解得到了二维片层自组装为3D微球结构的Co_(3)O_(4)复合氮掺杂碳材料(Co_(3)O_(4)/NC)。研究表明,由于3D微球结构、高温热解促进材料石墨化以及Co与杂原子N的协同作用,Co_(3)O_(4)/NC展现了优异的电催化析氢活性,起始电位从-0.92 V (vs.RHE)降到了-0.27 V (vs.RHE),电流密度提升为TAPA-TFB-COF的14倍,Tafel斜率仅为151 mV·dec^(-1),电化学反应电荷转移电阻(R_(ct))小至80.8Ω。
基金This work was supported by the National Natural Science Foundation of China(Nos.51772036 and 51572040)the Fundamental Research Funds for the Central Universities(Nos.2019CDXZWL001 and 2020CDCGJ005).
文摘Enhancement of supercapacitors(SCs)with high-energy density and high-power density is still a great challenge.In this paper,a facile strategy for in situ anchoring of Co_(3)O_(4) particles on N doped carbon cloth(pCoNCC)is reported.Due to the interaction of the doped N and Co_(3)O_(4),the electrochemical performance improves significantly,reaching 1,940.13 mF·cm^(−2) at 1 mA·cm^(−2) and energy density of 172.46μWh·cm^(−2) at the power density of 400μW·cm^(−2),much larger than that without N doping electrode of 28.5 mF·cm^(−2).An aqueous symmetric supercapacitor(ASSC)assembled by two pCoNCC electrodes achieves a maximum energy density of 447.42μWh·cm^(−2) and a highest power density of 8,000μW·cm^(−2).Utilizing such a high-energy storage ASSC,a digital watch and a temperature-humidity detector are powered for nearly 1 and 2 h,respectively.Moreover,the ASSC displays a superb electrochemical stability of 87.7%retention after 10,000 cycles at 40 mA·cm^(−2).This work would provide a new sight to enhance active materials performance and be beneficial for the future energy storage and supply systems.
基金Acknowledgements This work was supported by the Thousand Talents Plan, the National Natural Science Foundation of China （Nos. 21473169, 21673215, and 51402283）, the Fundamental Research Funds for the Central Universities （Nos. WK2060030017 and WK2060190026）, and the startup funds from the University of Science and Technology of China. This work was also supported by Hefei Science Center （No. 2015HSC-UP010）.
文摘Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns. In this work, atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride （g-C3N4） using atomic layer deposition. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy （HAADF-STEM） confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle （NP） formation. During selective hydrogenation of acetylene in excess ethylene, the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/Al2O3 and Pd/SiO2 catalysts. In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement. More impressively, the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance. Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.
基金We greatly appreciate the support of the National Natural Science Foundation of China （Nos. 21475057, 21335004,） and the Program B tbr Outstanding PhD Candidates of Nanjing University. This work was also supported by the Program for New Century Excellent Talents in University （No. NCET-12-0256）.
文摘The preparation of highly active electrocatalysts with good durability and low cost for fuel cells is highly desir- able but still remains a significant challenge. Here we synthesized two dimensional （2D） C3N4 nanosheets supported palladium composites （C3N4/Pd） via a simple and convenient sonochemical approach. We have systematically stud- ied the electrocatalytic performance of as-prepared catalysts. We found that the prepared C3N4/Pd composites pos- sessed excellent catalytic activity and stability for oxygen reduction reaction （ORR） in alkaline media. Encourag- ingly, the C3N4/Pd catalysts exhibit the excellent electrocatalytic activity for methanol oxidation reaction （MOR） in alkaline media, even better than that of the commercial Pt/C catalyst, The excellent electrocatalytic performance of the 2D C3N4 nanosheets supported palladium composites catalysts results from their synergy effect between the ul- trathin substrate material with large surface area and excellent dispersion of palladium nanoparticles. This study demonstrates that sonochemical method opens up a new avenue for the preparation of electrocatalysts for fuel cells. We expect these materials are likely to find uses in a broad range of applications, for example, fuel cells, solar cells, batteries and other electrochemical analysis.
基金financially supported by the Key Research and Development Program of Hubei Province(2020BCA079)the National Natural Science Foundation of China(52173106)。
