The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing mul...The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site^(−1) at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.展开更多
An ultra-efficient electro-Fenton catalyst with porous carbon coated Fe-Mo metal(FeMo@PC),was prepared by calcining MIL-53(Fe)@MoO_(3).This FeMo@PC-2 exhibited impressive catalytic performance for sulfamethazine(SMT)d...An ultra-efficient electro-Fenton catalyst with porous carbon coated Fe-Mo metal(FeMo@PC),was prepared by calcining MIL-53(Fe)@MoO_(3).This FeMo@PC-2 exhibited impressive catalytic performance for sulfamethazine(SMT)degradation with a high turnover frequency value(7.89 L/(g·min)),much better than most of reported catalysts.The mineralization current efficiency and electric energy consumption were 83.2%and 0.03 kWh/gTOC,respectively,at lowcurrent(5mA)and small dosage of catalyst(25.0mg/L).The removal rate of heterogeneous electro-Fenton(Hetero-EF)process catalyzed by FeMo@PC-2 was 4.58 times that of Fe@PC/Hetero-EF process.Because the internal-micro-electrolysis occurred between PC and Fe0,while the co-catalysis of Mo accelerated the rate-limiting step of the Fe^(3+)/Fe^(2+) cycle and greatly improved the H_(2)O_(2)utilization efficiency.The results of radical scavenger experiments and electron paramagnetic resonance confirmed the main role of surface-bound hydroxyl radical oxidation.This process was feasible to remove diverse organic contaminants such as phenol,2,4-dichlorophenoxyacetic acid,carbamazepine and SMT.This paper enlightened the importance of the doped Mo,which could greatly improve the activity of the iron-carbon heterogeneous catalyst derived from metal-organic frameworks in EF process for efficient removal of organic contaminants.展开更多
In spite of the tumor microenvironments responsive cancer therapy based on Fenton reaction(i.e.,chemodynamic therapy,CDT)has been attracted more attentions in recent years,the limited Fenton reaction efficiency is the...In spite of the tumor microenvironments responsive cancer therapy based on Fenton reaction(i.e.,chemodynamic therapy,CDT)has been attracted more attentions in recent years,the limited Fenton reaction efficiency is the important obstacle to further application in clinic.Herein,we synthesized novel FeO/MoS2 nanocomposites modified by bovine serum albumin(FeO/MoS2-BSA)with boosted Fenton reaction efficiency by the synergistic effect of co-catalyze and photothermal effect of MoS2 nanosheets triggered by the second near-infrared(NIR II)light.In the tumor microenvironments,the MoS2 nanosheets not only can accelerate the conversion of Fe3+ions to Fe2+ions by Mo4+ions on their surface to improve Fenton reaction efficiency,but also endow FeO/MoS2-BSA with good photothermal performances for photothermal-enhanced CDT and photothermal therapy(PTT).Consequently,benefiting from the synergetic-enhanced CDT/PTT,the tumors are eradicated completely in vivo.This work provides innovative synergistic strategy for constructing nanocomposites for highly efficient CDT.展开更多
A one-pot synthesis of vicinal diamines using indoles,azoles and phenothiazines in a tandem multi-component reaction is developed.The utilization of a copper-iodine co-catalytic system enables the generation of a dive...A one-pot synthesis of vicinal diamines using indoles,azoles and phenothiazines in a tandem multi-component reaction is developed.The utilization of a copper-iodine co-catalytic system enables the generation of a diverse range of vicinal diaminoindoles with good selectivity and moderate to good yields.An attractive aspect of this method is that it can be conducted under mild and environmentally friendly conditions,showcasing its potential as an alternative approach for synthesizing vicinal diamines.Moreover,the use of a multicomponent tandem reaction highlights the power and versatility of such strategies in synthetic chemistry.展开更多
Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions,but the low selectivity of styrene is difficult to be improved with by-products of ...Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions,but the low selectivity of styrene is difficult to be improved with by-products of ethylbenzene and xylene.In this study,a new way is introduced to improve the catalytic performance by means of assisting basic compounds as co-catalysts during the toluene side-chain alkylation with methanol to styrene.As a result,high activity of side-chain alkylation appears over the basic Cs-modified zeolite catalysts prepared by ion exchange and impregnation methods.This high performance should be mainly attributed to two co-catalysis actions:(1)the promotion of basic compounds for methanol dehydrogenation to formaldehyde as the intermediate for side-chain alkylation;(2)the suppression of the styrene transfer hydrogenation on basic Cs-modified zeolites to avoid the formation of ethylbenzene.Especially for Cs_(2)O/CsX-ex catalyst,the addition of 2%mol/mol 2-picoline in reaction mixture could achieve both 12.3%toluene conversion and 84.1%styrene selectivity.Whereas the higher concentration of 2-picoline(>6%mol/mol)caused an inhibition to the catalytic activity because the excessive basic compound poisoned the combined acid-base pathway required for the side-chain alkylation process.In addition,two possible side-chain alkylation reaction routes on Cs-modified zeolite under the different 2-picoline absorption were described.展开更多
Triphenylmethane(tpm) derivatives(e.g. tpm CV) have threatened the safety of the aquatic environment due to the potential toxicity and carcinogenicity. In this study, the novel ultrasonic/persulfate/chlorite(US/S_(2)O...Triphenylmethane(tpm) derivatives(e.g. tpm CV) have threatened the safety of the aquatic environment due to the potential toxicity and carcinogenicity. In this study, the novel ultrasonic/persulfate/chlorite(US/S_(2)O_(8)^(2-)/ClO_(2)^(-)) oxidation process was developed for the effective removal of tpm CV in wastewater. The apparent non-integer kinetics( n around 1.20) of tpm CV degradation under different factors( R^(2)_(Adj) > 0.990) were investigated, respectively. Inhibiting effects of anions were greater than those of cations(except Fe(Ⅱ/Ⅲ)). The adding of micromolecule organic acids could regulate degradation towards positive direction. The double response surface methodology(RSM) was designed to optimize tpm CV removal process, and the acoustic-piezoelectric interaction was simulated to determine the propagation process of acoustic wave in the reactor. The possible degradation pathway was explored to mainly include carbonylation, carboxylation, and demethylation. The estimated effectivemean temperature at the bubble-water interface was calculated from 721 to 566 K after introducing the ClO_(2)^(-), however, the adsorption or partitioning capacity of tpm CV in the reactive zone was widened from 0.0218 to 0.0982. The proposed co-catalysis of US/S_(2)O_(8)^(2-)/ClO_(2)^(-)was based on the determined active species mainly including ClO_(2), SO_(4)·^(-), and ·OH. Compared with other US-based processes, the operating cost(3.97 $/m^(3)) of US/S_(2)O_(8)^(2-)/ClO_(2)^(-)with the EE/O value(16.8 k Wh/m^(3)) was relatively reduced.展开更多
基金financially supported in China by the Natural Science Funds for Distinguished Young Scholar of Heilongjiang Province (No. JC2018004)
文摘The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site^(−1) at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.
基金supported by National Key R&D Program International Cooperation Project(No.2021YFE0106500)Natural Science Foundation of China(Nos.52170085 and 21976096)+2 种基金Tianjin Development Program for Innovation and Entrepreneurship,Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)Tianjin Post-graduate Students Research and Innovation Project(No.2019YJSB075)Fundamental Research Funds for the Central Universities,Nankai University(No.63221313).
文摘An ultra-efficient electro-Fenton catalyst with porous carbon coated Fe-Mo metal(FeMo@PC),was prepared by calcining MIL-53(Fe)@MoO_(3).This FeMo@PC-2 exhibited impressive catalytic performance for sulfamethazine(SMT)degradation with a high turnover frequency value(7.89 L/(g·min)),much better than most of reported catalysts.The mineralization current efficiency and electric energy consumption were 83.2%and 0.03 kWh/gTOC,respectively,at lowcurrent(5mA)and small dosage of catalyst(25.0mg/L).The removal rate of heterogeneous electro-Fenton(Hetero-EF)process catalyzed by FeMo@PC-2 was 4.58 times that of Fe@PC/Hetero-EF process.Because the internal-micro-electrolysis occurred between PC and Fe0,while the co-catalysis of Mo accelerated the rate-limiting step of the Fe^(3+)/Fe^(2+) cycle and greatly improved the H_(2)O_(2)utilization efficiency.The results of radical scavenger experiments and electron paramagnetic resonance confirmed the main role of surface-bound hydroxyl radical oxidation.This process was feasible to remove diverse organic contaminants such as phenol,2,4-dichlorophenoxyacetic acid,carbamazepine and SMT.This paper enlightened the importance of the doped Mo,which could greatly improve the activity of the iron-carbon heterogeneous catalyst derived from metal-organic frameworks in EF process for efficient removal of organic contaminants.
基金This work was supported by the financial aid from the National Natural Science Foundation of China(Grant Nos.51502284,21834007,21521092,21590794,and 21673220)the Program of Science and Technology Development Plan of Jilin Province of China(No.20170101186JC)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB20030300)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2019232).
文摘In spite of the tumor microenvironments responsive cancer therapy based on Fenton reaction(i.e.,chemodynamic therapy,CDT)has been attracted more attentions in recent years,the limited Fenton reaction efficiency is the important obstacle to further application in clinic.Herein,we synthesized novel FeO/MoS2 nanocomposites modified by bovine serum albumin(FeO/MoS2-BSA)with boosted Fenton reaction efficiency by the synergistic effect of co-catalyze and photothermal effect of MoS2 nanosheets triggered by the second near-infrared(NIR II)light.In the tumor microenvironments,the MoS2 nanosheets not only can accelerate the conversion of Fe3+ions to Fe2+ions by Mo4+ions on their surface to improve Fenton reaction efficiency,but also endow FeO/MoS2-BSA with good photothermal performances for photothermal-enhanced CDT and photothermal therapy(PTT).Consequently,benefiting from the synergetic-enhanced CDT/PTT,the tumors are eradicated completely in vivo.This work provides innovative synergistic strategy for constructing nanocomposites for highly efficient CDT.
基金the National Natural Science Foundation of China(22201048)the Natural Science Foundation of Guangxi Province(2022GXNSFBA035480)+1 种基金the Specific Research Project of Guangxi for Research Bases and Talents(2022AC21099)the Start-up Fund of Guangxi University(A3040051013)for financial support.
文摘A one-pot synthesis of vicinal diamines using indoles,azoles and phenothiazines in a tandem multi-component reaction is developed.The utilization of a copper-iodine co-catalytic system enables the generation of a diverse range of vicinal diaminoindoles with good selectivity and moderate to good yields.An attractive aspect of this method is that it can be conducted under mild and environmentally friendly conditions,showcasing its potential as an alternative approach for synthesizing vicinal diamines.Moreover,the use of a multicomponent tandem reaction highlights the power and versatility of such strategies in synthetic chemistry.
基金Supported by the National Natural Science Foundation of China(#91534115).
文摘Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions,but the low selectivity of styrene is difficult to be improved with by-products of ethylbenzene and xylene.In this study,a new way is introduced to improve the catalytic performance by means of assisting basic compounds as co-catalysts during the toluene side-chain alkylation with methanol to styrene.As a result,high activity of side-chain alkylation appears over the basic Cs-modified zeolite catalysts prepared by ion exchange and impregnation methods.This high performance should be mainly attributed to two co-catalysis actions:(1)the promotion of basic compounds for methanol dehydrogenation to formaldehyde as the intermediate for side-chain alkylation;(2)the suppression of the styrene transfer hydrogenation on basic Cs-modified zeolites to avoid the formation of ethylbenzene.Especially for Cs_(2)O/CsX-ex catalyst,the addition of 2%mol/mol 2-picoline in reaction mixture could achieve both 12.3%toluene conversion and 84.1%styrene selectivity.Whereas the higher concentration of 2-picoline(>6%mol/mol)caused an inhibition to the catalytic activity because the excessive basic compound poisoned the combined acid-base pathway required for the side-chain alkylation process.In addition,two possible side-chain alkylation reaction routes on Cs-modified zeolite under the different 2-picoline absorption were described.
基金supported by the State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (No. 2019DX08)the Natural Science Foundation of Shandong Province of China (No. ZR2019QEE012)。
文摘Triphenylmethane(tpm) derivatives(e.g. tpm CV) have threatened the safety of the aquatic environment due to the potential toxicity and carcinogenicity. In this study, the novel ultrasonic/persulfate/chlorite(US/S_(2)O_(8)^(2-)/ClO_(2)^(-)) oxidation process was developed for the effective removal of tpm CV in wastewater. The apparent non-integer kinetics( n around 1.20) of tpm CV degradation under different factors( R^(2)_(Adj) > 0.990) were investigated, respectively. Inhibiting effects of anions were greater than those of cations(except Fe(Ⅱ/Ⅲ)). The adding of micromolecule organic acids could regulate degradation towards positive direction. The double response surface methodology(RSM) was designed to optimize tpm CV removal process, and the acoustic-piezoelectric interaction was simulated to determine the propagation process of acoustic wave in the reactor. The possible degradation pathway was explored to mainly include carbonylation, carboxylation, and demethylation. The estimated effectivemean temperature at the bubble-water interface was calculated from 721 to 566 K after introducing the ClO_(2)^(-), however, the adsorption or partitioning capacity of tpm CV in the reactive zone was widened from 0.0218 to 0.0982. The proposed co-catalysis of US/S_(2)O_(8)^(2-)/ClO_(2)^(-)was based on the determined active species mainly including ClO_(2), SO_(4)·^(-), and ·OH. Compared with other US-based processes, the operating cost(3.97 $/m^(3)) of US/S_(2)O_(8)^(2-)/ClO_(2)^(-)with the EE/O value(16.8 k Wh/m^(3)) was relatively reduced.
