Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch ...Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch procedure and continuous-flow procedure) were used to study the variations of reaction processing. The heterogeneous catalysts presented excellent reactivity and recyclability for iodobenzene and bromobenzene substrates in batch mode, which can be attributed to stabilization of Pd nanoparticles by the thiol and amino groups on the AC supports. However, significant dehalogenation in the reaction mixture and Pd leaching from the heterogeneous catalysts were observed in continuous-flow mode.This unique phenomenon in continuous-flow mode resulted in a dramatic decline in reaction selectivity and durability of heterogeneous catalysts comparing with that of batch mode. In addition, the heterogeneous Pd catalysts with thiol-and amino-modified AC supports exhibited different reactivity and durability in batch and continuous-flow mode owing to the difference of interaction between Pd species and AC supports.展开更多
The decontaminating of catalysts nickel on kieselguhr, activated aluminum oxide and palladium catalyst LD-265 agent’s nature was analyzed. The possibility of catalyst’s regeneration was examined using supercritical ...The decontaminating of catalysts nickel on kieselguhr, activated aluminum oxide and palladium catalyst LD-265 agent’s nature was analyzed. The possibility of catalyst’s regeneration was examined using supercritical CO2 extraction. Regeneration of coked catalysts was carried out at 70oC and 150oC in the pressure range 10 - 30 MPa by pure and modified supercritical CO2. Methanol and dimethylsulfoxide were used as modifiers (co-solvents) of supercritical CO2. The kinetics of supercritical CO2 regeneration process was studied. The activity of regenerated catalysts was measured.展开更多
Results of research of supercritical fluid CO2-impregnation process (the static mode) within a problem of synthesis of the palladium catalyst are given. The kinetics of process is characterized in the pressure range f...Results of research of supercritical fluid CO2-impregnation process (the static mode) within a problem of synthesis of the palladium catalyst are given. The kinetics of process is characterized in the pressure range from 15.0 to 35.0 MPa on temperatures 308.15?K, 313.15?K, 318.15?K, 323.15?K, 328.15?K and 333.15?K. Results of surface assessment and activity measurements of the catalyst samples synthesized by supercritical СO2-impregnation of aluminum oxide suggest competitiveness of the discussed approach in comparison to traditional methods.展开更多
For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at...For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at < 100 °C, and good to excellent yields were obtained.展开更多
A novel complex Pd（C4H2O4）（C4H8N2）0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate （DPC） by oxidative carbonylation of phenol....A novel complex Pd（C4H2O4）（C4H8N2）0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate （DPC） by oxidative carbonylation of phenol. In the reaction system of Pd（C4H2O4）（C4H8N2）0.5/Cu（OAc）2/ tetrabutylammonium bromide/ hydroquinone/ 4A molecular sieves, the effect of reaction temperature, time and CO pressure on catalytic activity were investigated, and the results revealed that the catalyst could catalyze oxidative carbonylation of phenol effectively. Under suitable reaction conditions of T=90℃, t=4 h, p（O2）=0.3 MPa, p（CO）=3.9 MPa and CH2Cl2 as solvent, the turnover number （TON） of diphenyl carbonate can reach about 13.50 （mol-DPC/mol-Pd）, which is higher than the TON for oure PdCl2 under the same reaction conditions.展开更多
We have dispersed individual Pd atoms onto ZnO nanowires(NWs)as single‐atom catalysts(SACs)and evaluated their catalytic performance for several selected catalytic reactions.The Pd1/ZnO SAC is highly active,stable,an...We have dispersed individual Pd atoms onto ZnO nanowires(NWs)as single‐atom catalysts(SACs)and evaluated their catalytic performance for several selected catalytic reactions.The Pd1/ZnO SAC is highly active,stable,and selective towards CO2for steam reforming of methanol to produce hydrogen.This catalyst system is active for oxidation of CO and H2but performs poorly for preferential oxidation of CO in hydrogen‐rich stream primarily due to the strong competitive oxidation of H2on ZnO supported Pd1atoms.At ambient pressure,reverse water‐gas‐shift reaction occurs on the Pd1/ZnO SAC.This series of tests of catalytic reactions clearly demonstrate the importance of selecting the appropriate metal and support to develop SACs for catalytic transformation of molecules.展开更多
A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst（Ph-SBA-15-PPh_3-Pd） exhibi...A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst（Ph-SBA-15-PPh_3-Pd） exhibited high catalytic activity for the Heck reaction of 4-nitrobromobenzene with methyl acrylate.The catalyst can be reused several times without a loss of activity.展开更多
基金the support of the National Natural Science Foundation of China (20222809, 21978146)TsinghuaFoshan Innovation Special Fund (2021THFS0214)。
文摘Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch procedure and continuous-flow procedure) were used to study the variations of reaction processing. The heterogeneous catalysts presented excellent reactivity and recyclability for iodobenzene and bromobenzene substrates in batch mode, which can be attributed to stabilization of Pd nanoparticles by the thiol and amino groups on the AC supports. However, significant dehalogenation in the reaction mixture and Pd leaching from the heterogeneous catalysts were observed in continuous-flow mode.This unique phenomenon in continuous-flow mode resulted in a dramatic decline in reaction selectivity and durability of heterogeneous catalysts comparing with that of batch mode. In addition, the heterogeneous Pd catalysts with thiol-and amino-modified AC supports exhibited different reactivity and durability in batch and continuous-flow mode owing to the difference of interaction between Pd species and AC supports.
基金supported by financial support from the National Science Foundation of China (21133010, 21473223, 51221264, 21261160487, 21411130120, 21503241, 91545119, 91545110)"Strategic Priority Research Program" of the Chinese Academy of Sciences, Grant no. XDA09030103CAS/SAFEA International Partnership Program for Creative Research Teams
文摘The decontaminating of catalysts nickel on kieselguhr, activated aluminum oxide and palladium catalyst LD-265 agent’s nature was analyzed. The possibility of catalyst’s regeneration was examined using supercritical CO2 extraction. Regeneration of coked catalysts was carried out at 70oC and 150oC in the pressure range 10 - 30 MPa by pure and modified supercritical CO2. Methanol and dimethylsulfoxide were used as modifiers (co-solvents) of supercritical CO2. The kinetics of supercritical CO2 regeneration process was studied. The activity of regenerated catalysts was measured.
文摘Results of research of supercritical fluid CO2-impregnation process (the static mode) within a problem of synthesis of the palladium catalyst are given. The kinetics of process is characterized in the pressure range from 15.0 to 35.0 MPa on temperatures 308.15?K, 313.15?K, 318.15?K, 323.15?K, 328.15?K and 333.15?K. Results of surface assessment and activity measurements of the catalyst samples synthesized by supercritical СO2-impregnation of aluminum oxide suggest competitiveness of the discussed approach in comparison to traditional methods.
基金supported by the National Natural Science Foundation of China(91745106,21633013)the Major Projects of the National Natural Science Foundation of Gansu,China(18JR4RA001)+1 种基金the Youth Innovation Promotion Association CAS(2019409)Fujian Institute of Innovation,CAS and Key Research Program of Frontier Sciences of CAS(QYZDJ-SSW-SLH051)~~
文摘For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at < 100 °C, and good to excellent yields were obtained.
基金Supported by the National Natural Science Foundation of China （20636030）, Tlanjin Natural Science Foundation （07JCZDJC 00100）.
文摘A novel complex Pd（C4H2O4）（C4H8N2）0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate （DPC） by oxidative carbonylation of phenol. In the reaction system of Pd（C4H2O4）（C4H8N2）0.5/Cu（OAc）2/ tetrabutylammonium bromide/ hydroquinone/ 4A molecular sieves, the effect of reaction temperature, time and CO pressure on catalytic activity were investigated, and the results revealed that the catalyst could catalyze oxidative carbonylation of phenol effectively. Under suitable reaction conditions of T=90℃, t=4 h, p（O2）=0.3 MPa, p（CO）=3.9 MPa and CH2Cl2 as solvent, the turnover number （TON） of diphenyl carbonate can reach about 13.50 （mol-DPC/mol-Pd）, which is higher than the TON for oure PdCl2 under the same reaction conditions.
基金funded by the National Science Foundation (CHE-1465057)
文摘We have dispersed individual Pd atoms onto ZnO nanowires(NWs)as single‐atom catalysts(SACs)and evaluated their catalytic performance for several selected catalytic reactions.The Pd1/ZnO SAC is highly active,stable,and selective towards CO2for steam reforming of methanol to produce hydrogen.This catalyst system is active for oxidation of CO and H2but performs poorly for preferential oxidation of CO in hydrogen‐rich stream primarily due to the strong competitive oxidation of H2on ZnO supported Pd1atoms.At ambient pressure,reverse water‐gas‐shift reaction occurs on the Pd1/ZnO SAC.This series of tests of catalytic reactions clearly demonstrate the importance of selecting the appropriate metal and support to develop SACs for catalytic transformation of molecules.
基金National Natural Science Foundation of China(No.20603005)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20090041110012) for their financial support
文摘A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst（Ph-SBA-15-PPh_3-Pd） exhibited high catalytic activity for the Heck reaction of 4-nitrobromobenzene with methyl acrylate.The catalyst can be reused several times without a loss of activity.
