MoS_(2)nanoflowers are favored for their potential in the production of elemental sulfur due to abundant surface area and good catalytic performance for reducing SO_(2).A novel synthetic strategy of porous Al_(2)O_(3)...MoS_(2)nanoflowers are favored for their potential in the production of elemental sulfur due to abundant surface area and good catalytic performance for reducing SO_(2).A novel synthetic strategy of porous Al_(2)O_(3)supported on the MoS_(2)with nanoflower structure was proposed.The effects of preparation concentration,calcination atmosphere,Al_(2)O_(3)contents on the growth of catalysts with nanoflower structure were systematically studied via X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM),Fourier transform infrared(FTIR)spectroscopy,Brunauer–Emmett–Teller(BET).The surface area was increased to 295.502 m^(2)/g and the amount of Lewis acid on the surface of the Al_(2)O_(3)/MoS_(2)catalyst was increased by adjusting the ratio of Al/Mo.The porous and nanoflower structures of Al_(2)O_(3)/MoS_(2)catalysts promoted the sulfur selectivity without inhibiting the catalytic performance of MoS_(2).The conversion of SO_(2)and the selectivity of sulfur were 100%and 92%after 100 h life evaluation.展开更多
For the first time a mathematical modelling of porous catalyst particles subject to both internal mass concentration gradients as well as temperature gradients, in endothermic or exothermic reactions has been reported...For the first time a mathematical modelling of porous catalyst particles subject to both internal mass concentration gradients as well as temperature gradients, in endothermic or exothermic reactions has been reported. This model contains a non-linear mass balance equation which is related to rate expression. This paper presents an approximate analytical method (Modified Adomian decomposition method) to solve the non-linear differential equations for chemical kinetics with diffusion effects. A simple and closed form of expressions pertaining to substrate concentration and utilization factor is presented for all value of diffusion parameters. These analytical results are compared with numerical results and found to be in good agreement.展开更多
To commercialize fuel cells and metal-air batteries, cost-effective, highly active catalysts for the oxygen reduction reaction (ORR) must be developed. Herein, we describe the development of low-cost, heteroatom (N...To commercialize fuel cells and metal-air batteries, cost-effective, highly active catalysts for the oxygen reduction reaction (ORR) must be developed. Herein, we describe the development of low-cost, heteroatom (N, P, Fe) ternary-doped, porous carbons (HDPC). These materials are prepared by one-step pyrolysis of natural tea leaves treated with an iron salt, without any chemical and physical activation. The natural structure of the tea leaves provide a 3D hierarchical porous structure after carbonization. Moreover, heteroatom containing organic compounds in tea leaves act as precursors to functionalize the resultant carbon frameworks. In addition, we found that the polyphenols present in tea leaves act as ligands, reacting with Fe ions to form coordination compounds; these complexes acted as the precursors for Fe and N active sites. After pyrolysis, the as-prepared HDPC electrocatalysts, especially HDPC-800 (pyrolyzed at 800℃), had more positive onsets, half-wave potentials, and higher catalytic activities for the ORR, which proceeds via a direct four-electron reaction pathway in alkaline media, similar to commercial Pt/C catalysts. Furthermore, HDPC-X also showed enhanced durability and better tolerance to methanol crossover and CO poisoning effects in comparison to commercial Pt/C, making them promising alternatives for state-of-the-art ORR electrocatalysts for electrochemical energy conversion. The method used here provides valuable guidelines for the design of high-performance ORR electrocatalysts from natural sources at the industrial scale.展开更多
Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniqu...Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniques. The photocatalytic activities of the BiVO4 materials were evaluated for the degradation of Methyl Orange under visible-light irradiation. It is observed that pH value and surfactant exerted a great effect on the morphology and pore structure of the BiVO4 product. Spherical BiVO4 with porous structures, flower-cluster-like BiVO4, and flower-bundle-like BiVO4 were generated hydrothermally at 100°C with poly(vinyl pyrrolidone) (PVP) and urea (pH = 2) and at 160°C with NaHCO3 (pH = 7 and 8), respectively. The PVP-derived BiVO4 showed much higher surface areas (5.0-8.4 m2/g) and narrower bandgap energies (2.45-2.49 eV). The best photocatalytic performance of the spherical BiVO4 material with a surface area of 8.4 m2/g was associated with its higher surface area, narrower bandgap energy, higher surface oxygen vacancy density, and unique porous architecture.展开更多
Hydroformylation has been widely used in industry to manufacture high value-added aldehydes and alcohols, and is considered as the largest homogenously catalyzed process in industry. However, this process often suffer...Hydroformylation has been widely used in industry to manufacture high value-added aldehydes and alcohols, and is considered as the largest homogenously catalyzed process in industry. However, this process often suffers from complicated operation and the difficulty in catalyst recycling. It is highly desirable to develop a heterogeneous catalyst that enables the catalyst recovery without sacrificing the activity and selectivity. There are two strategies to afford such a catalyst for the hydrofromylation: immobilized catalysts on solid support and porous organic ligand (POL)-supported catalysts. In the latter, high concentration of phosphine ligands in the catalyst framework is favorable for the high dispersion of rhodium species and the formation of Rh-P multiple bonds, which endow the catalysts with high activity and stability respectively. Besides, the high linear regioselectivity could be achieved through the copolymerization of vinyl functionalized bidentate ligand (vinyl biphephos) and monodentate ligand (3vPPh3) into the catalyst framework. The newly-emerging POL-supported catalysts have great perspectives in the industrial hydroformylation.展开更多
The mechanical strength of solid catalysts is one of the key parameters for reliable and efficient perform-ance of a fixed bed reactor. Some recent developments and their basic mechanics within this context are review...The mechanical strength of solid catalysts is one of the key parameters for reliable and efficient perform-ance of a fixed bed reactor. Some recent developments and their basic mechanics within this context are reviewed. The main concepts discussed are brittle fracture which leads to the mechanical failure of the catalyst pellets, measurement and statistical properties of the catalyst strength data, and mechanical reliability of the catalyst pellets and their packed bed. The scientific basis for the issues on the catalyst mechanical properties calls yet for further elucidation and ad-vancement.展开更多
Heteroatom doping, precise composition control and rational morphology design are efficient strategies for producing novel nanocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Herein, a cost-effectiv...Heteroatom doping, precise composition control and rational morphology design are efficient strategies for producing novel nanocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Herein, a cost-effective approach to synthesize nitrogen- and sulfur-codoped carbon nanowire aerogels using a hard templating method is proposed. The aerogels prepared using a combination of hydrothermal treatment and carbonization exhibit good catalytic activity for the ORR in alkaline solution. At the optimal annealing temperature and mass ratio between the nitrogen and sulfur precursors, the resultant aerogels show comparable electrocatalytic activity to that of a commercial Pt/C catalyst for the ORR. Importantly, the optimized catalyst shows much better long-term stability and satisfactory tolerance for the methanol crossover effect. These codoped aerogels are expected to have potential applications in fuel cells.展开更多
基金the National Natural Science Fund for Distinguished Young Scholars of China(No.22025803).
文摘MoS_(2)nanoflowers are favored for their potential in the production of elemental sulfur due to abundant surface area and good catalytic performance for reducing SO_(2).A novel synthetic strategy of porous Al_(2)O_(3)supported on the MoS_(2)with nanoflower structure was proposed.The effects of preparation concentration,calcination atmosphere,Al_(2)O_(3)contents on the growth of catalysts with nanoflower structure were systematically studied via X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM),Fourier transform infrared(FTIR)spectroscopy,Brunauer–Emmett–Teller(BET).The surface area was increased to 295.502 m^(2)/g and the amount of Lewis acid on the surface of the Al_(2)O_(3)/MoS_(2)catalyst was increased by adjusting the ratio of Al/Mo.The porous and nanoflower structures of Al_(2)O_(3)/MoS_(2)catalysts promoted the sulfur selectivity without inhibiting the catalytic performance of MoS_(2).The conversion of SO_(2)and the selectivity of sulfur were 100%and 92%after 100 h life evaluation.
文摘For the first time a mathematical modelling of porous catalyst particles subject to both internal mass concentration gradients as well as temperature gradients, in endothermic or exothermic reactions has been reported. This model contains a non-linear mass balance equation which is related to rate expression. This paper presents an approximate analytical method (Modified Adomian decomposition method) to solve the non-linear differential equations for chemical kinetics with diffusion effects. A simple and closed form of expressions pertaining to substrate concentration and utilization factor is presented for all value of diffusion parameters. These analytical results are compared with numerical results and found to be in good agreement.
基金Acknowledgements The authors thank the financial support by the National Natural Science Foundation of China (No. 51273008 and 51473008), the National High-Tech Research and Development Program (No. 2012AA030305), the National Basic Research Program (No. 2012CB933200), and NSF (No. CMMI-1400274 and AIR-IIP-1343270).
文摘To commercialize fuel cells and metal-air batteries, cost-effective, highly active catalysts for the oxygen reduction reaction (ORR) must be developed. Herein, we describe the development of low-cost, heteroatom (N, P, Fe) ternary-doped, porous carbons (HDPC). These materials are prepared by one-step pyrolysis of natural tea leaves treated with an iron salt, without any chemical and physical activation. The natural structure of the tea leaves provide a 3D hierarchical porous structure after carbonization. Moreover, heteroatom containing organic compounds in tea leaves act as precursors to functionalize the resultant carbon frameworks. In addition, we found that the polyphenols present in tea leaves act as ligands, reacting with Fe ions to form coordination compounds; these complexes acted as the precursors for Fe and N active sites. After pyrolysis, the as-prepared HDPC electrocatalysts, especially HDPC-800 (pyrolyzed at 800℃), had more positive onsets, half-wave potentials, and higher catalytic activities for the ORR, which proceeds via a direct four-electron reaction pathway in alkaline media, similar to commercial Pt/C catalysts. Furthermore, HDPC-X also showed enhanced durability and better tolerance to methanol crossover and CO poisoning effects in comparison to commercial Pt/C, making them promising alternatives for state-of-the-art ORR electrocatalysts for electrochemical energy conversion. The method used here provides valuable guidelines for the design of high-performance ORR electrocatalysts from natural sources at the industrial scale.
基金supported by the National Natural Science Foundation of China (No. 20973017, 21077007)the Creative Research Foundation of Beijing University of Technology (No. 00500054R4003, 005000543111501)+2 种基金the HiTech Research and Development Program (863)of China (No. 2009AA063201)the Funding Projectfor Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (No. PHR200907105, PHR201007105,PHR201107104)the Hong Kong Baptist University (FRG2/09-10/023)
文摘Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniques. The photocatalytic activities of the BiVO4 materials were evaluated for the degradation of Methyl Orange under visible-light irradiation. It is observed that pH value and surfactant exerted a great effect on the morphology and pore structure of the BiVO4 product. Spherical BiVO4 with porous structures, flower-cluster-like BiVO4, and flower-bundle-like BiVO4 were generated hydrothermally at 100°C with poly(vinyl pyrrolidone) (PVP) and urea (pH = 2) and at 160°C with NaHCO3 (pH = 7 and 8), respectively. The PVP-derived BiVO4 showed much higher surface areas (5.0-8.4 m2/g) and narrower bandgap energies (2.45-2.49 eV). The best photocatalytic performance of the spherical BiVO4 material with a surface area of 8.4 m2/g was associated with its higher surface area, narrower bandgap energy, higher surface oxygen vacancy density, and unique porous architecture.
基金Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant Nos. 21273227 and 21403258) and the Strategic Priority Research Program of the Chinese Academy of Science (Grant Nos XDB 17020400).
文摘Hydroformylation has been widely used in industry to manufacture high value-added aldehydes and alcohols, and is considered as the largest homogenously catalyzed process in industry. However, this process often suffers from complicated operation and the difficulty in catalyst recycling. It is highly desirable to develop a heterogeneous catalyst that enables the catalyst recovery without sacrificing the activity and selectivity. There are two strategies to afford such a catalyst for the hydrofromylation: immobilized catalysts on solid support and porous organic ligand (POL)-supported catalysts. In the latter, high concentration of phosphine ligands in the catalyst framework is favorable for the high dispersion of rhodium species and the formation of Rh-P multiple bonds, which endow the catalysts with high activity and stability respectively. Besides, the high linear regioselectivity could be achieved through the copolymerization of vinyl functionalized bidentate ligand (vinyl biphephos) and monodentate ligand (3vPPh3) into the catalyst framework. The newly-emerging POL-supported catalysts have great perspectives in the industrial hydroformylation.
文摘The mechanical strength of solid catalysts is one of the key parameters for reliable and efficient perform-ance of a fixed bed reactor. Some recent developments and their basic mechanics within this context are reviewed. The main concepts discussed are brittle fracture which leads to the mechanical failure of the catalyst pellets, measurement and statistical properties of the catalyst strength data, and mechanical reliability of the catalyst pellets and their packed bed. The scientific basis for the issues on the catalyst mechanical properties calls yet for further elucidation and ad-vancement.
文摘Heteroatom doping, precise composition control and rational morphology design are efficient strategies for producing novel nanocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Herein, a cost-effective approach to synthesize nitrogen- and sulfur-codoped carbon nanowire aerogels using a hard templating method is proposed. The aerogels prepared using a combination of hydrothermal treatment and carbonization exhibit good catalytic activity for the ORR in alkaline solution. At the optimal annealing temperature and mass ratio between the nitrogen and sulfur precursors, the resultant aerogels show comparable electrocatalytic activity to that of a commercial Pt/C catalyst for the ORR. Importantly, the optimized catalyst shows much better long-term stability and satisfactory tolerance for the methanol crossover effect. These codoped aerogels are expected to have potential applications in fuel cells.