The activation of HCl by cationic Au in the presence of C2H2 is important for the construction of active Au sites and in acetylene hydrochlorination.Here,we report a strategy for activating HCl by the Au-based support...The activation of HCl by cationic Au in the presence of C2H2 is important for the construction of active Au sites and in acetylene hydrochlorination.Here,we report a strategy for activating HCl by the Au-based supported ionic liquid phase(Au–SILP)technology with the[N(CN)2^–]anion.This strategy enables HCl to accept electrons from[N(CN)2^–]anions in Au–[N(CN)2^–]complexes rather than from pure[Bmim][N(CN)2],leading to notable improvement in both the reaction path and the stability of the catalyst without changing the reaction triggered by acetylene adsorption.Furthermore,the induction period of the Au–SILP catalyst was shown to be absent in the reaction process due to the high Au(III)content in the Au(Ⅲ)/Au(Ⅰ)site and the high substrate diffusion rate in the ionic liquid layer.This work provides a facile method to improve the stability of Au-based catalysts for acetylene hydrochlorination.展开更多
Rational design of catalytic sites to activate the C≡C bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by con...Rational design of catalytic sites to activate the C≡C bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by controlling the impregnation solutions. The π electrons flowing from acetylene to Cu site are facilitated over the electron-deficient Cu sites, achieving high activation of C≡C bond. The contradiction between the increased activation of acetylene required for enhanced catalytic activity and the resistance of Cu site to reduction by acetylene required for maintaining catalytic stability can be balanced by establishing strong interactions of Cu site with pyrrolic-N species. The catalytic activity displays a volcano shape scaling relationship as a function of Cu particle size. Tribasic copper chloride is concomitantly generated with the construction of electron-deficient Cu sites. The H–Cl bond of HCl can be activated over the tribasic copper chloride, accelerating the surface reaction of vinyl chloride production. This strategy of inducing electron deficiency provides new insight into the rational design of catalysts for the synthesis of vinyl chloride with a high catalytic performance.展开更多
In this study,a novel non-metallic carbon-based catalyst co-doped with boron and nitrogen(B,N)was successfully synthesized.By precisely controlling the carbonization temperature of a binary mixed ionic liquid,we selec...In this study,a novel non-metallic carbon-based catalyst co-doped with boron and nitrogen(B,N)was successfully synthesized.By precisely controlling the carbonization temperature of a binary mixed ionic liquid,we selectively modified the doping site structure,ultimately constructing a B,N co-doped frustrated Lewis acid-base pair catalyst.This catalyst exhibited remarkable catalytic activity,selectivity,and stability in the dehydrochlorination reaction of 1,1,2-trichloroethane(TCE).Detailed characterization and theoretical calculations revealed that the primary active center of this catalyst was the BN_(3)configuration.Compared to conventional graphitic N structures,the BN_(3)structure had a higher p-band center,ensuring superior adsorption and activation capabilities for TCE during the reaction.Within the BN_(3)site,three negatively charged nitrogen atoms acted as Lewis bases,while positively charged boron atoms acted as Lewis acids.This synergistic interaction facilitated the specific dissociation of chlorine and hydrogen atoms from TCE,significantly enhancing the 1,1-dichloroethene selectivity.Through this research,we not only explored the active site structure and catalytic mechanism of B,N co-doped catalysts in depth but also provided an efficient,selective,and stable catalyst for the dehydrochlorination of TCE,contributing significantly to the development of non-metallic catalysts.展开更多
Semi-hydrogenation of acetylene is of growing interest and popularity but subjects to a major challenge in selective hydrogenation to ethylene.Here,we report a strategy that uses graphdiyne(GDY)as a carrier to prepare...Semi-hydrogenation of acetylene is of growing interest and popularity but subjects to a major challenge in selective hydrogenation to ethylene.Here,we report a strategy that uses graphdiyne(GDY)as a carrier to prepare single-cluster catalysts(SCCs),which on average clusters composed of three atoms(denoted as Pd3 trimer)and applied it to the acetylene semihydrogenation in the presence of large amounts of ethylene.Based on experimental results and systematic quantum chemical research and computational screening,we found that there are multiple active Pd structures on GDY and the Pd3 trimer anchored on GDY is a specific and durable cluster with great potential for accurate and efficient heterogeneous catalysis.The synergetic effects between neighboring atoms in Pd trimer guarantee easy desorption of ethylene and the absence of unselective hydride species thereby preventing excessive hydrogenation to generate unwanted byproducts,which is a crucial mechanism for the excellent selectivity of the catalyst.This new method for precise synthesis Pd clusters provides accurate ways for designing selective hydrogenation catalysts at the atomic scale.展开更多
Dendritic cell(DC)tumor vaccines exert their antitumor effects through the induction of effector T cells.We recently identified Tc9 cells as a new potent antitumor effector T cell subset.However,approaches to direct D...Dendritic cell(DC)tumor vaccines exert their antitumor effects through the induction of effector T cells.We recently identified Tc9 cells as a new potent antitumor effector T cell subset.However,approaches to direct DCs to preferably prime antitumor Tc9 cells should be further exploited.Here,we demonstrate that the addition of interleukin(IL)-33 potently promotes the induction of Tc9 cells by DCs in vitro and in vivo.IL-33 treatment also drives the cytotoxic activities of DC-induced Tc9 cells.Notably,IL-33 treatment enhances cell survival and proliferation of DC-primed CD8+T cells.More importantly,the addition of IL-33 during in vitro priming of tumor-specific Tc9 cells by DCs increases the antitumor capability of Tc9 cells.Mechanistic studies demonstrated that IL-33 treatment inhibits exhaustive CD8+T cell differentiation by inhibiting PD-1 and 2B4 expression and increasing IL-2 and CD127(IL-7 receptor-α,IL-7Rα)expression in CD8+T cells.Finally,the addition of IL-33 further promotes the therapeutic efficacy of DC-based tumor vaccines in the OT-I mouse model.Our study demonstrates the important role of IL-33 in DC-induced Tc9 cell differentiation and antitumor immunity and may have important clinical implications.展开更多
A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4...A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.展开更多
In the process of acetylene hydrochlorination,the rapid deactivation of supported gold(Au)catalysts by acetylene is still a huge challenge.Here,we provide an innovative strategy for constructing an acetylene–deficien...In the process of acetylene hydrochlorination,the rapid deactivation of supported gold(Au)catalysts by acetylene is still a huge challenge.Here,we provide an innovative strategy for constructing an acetylene–deficient reaction phase on the active site by coating an ionic liquid film on the Au(H2O)/C surface.The reactant ratio of C2H2 to HCl in this acetylene–deficient reaction phase is 1:132,in contrast to the 1:1 M ratio in the gas phase,thus boosting the catalytic stability of Au(H2O)/C catalysts.The kinetic and theoretical analysis showed that the reduction of cationic gold by C2H2 and the generation of carbon deposition can be inhibited in this constructed reaction phase during reaction.The current work not only broadens the scope of supported Au catalysts in acetylene hydrochlorination,but also verifies the perspective of the tunability of stoichiometric balance,which can be used in other catalytic applications.展开更多
文摘The activation of HCl by cationic Au in the presence of C2H2 is important for the construction of active Au sites and in acetylene hydrochlorination.Here,we report a strategy for activating HCl by the Au-based supported ionic liquid phase(Au–SILP)technology with the[N(CN)2^–]anion.This strategy enables HCl to accept electrons from[N(CN)2^–]anions in Au–[N(CN)2^–]complexes rather than from pure[Bmim][N(CN)2],leading to notable improvement in both the reaction path and the stability of the catalyst without changing the reaction triggered by acetylene adsorption.Furthermore,the induction period of the Au–SILP catalyst was shown to be absent in the reaction process due to the high Au(III)content in the Au(Ⅲ)/Au(Ⅰ)site and the high substrate diffusion rate in the ionic liquid layer.This work provides a facile method to improve the stability of Au-based catalysts for acetylene hydrochlorination.
基金Financial support from the National Natural Science Foundation of China (NSFCgrant No.U20A20119,21606199,22078302,52070035)+3 种基金the Science and Technology Department of Zhejiang Province (LGG20B060004)the China Postdoctoral Science Foundation (2020M671791)the Jilin Province Scientific and the Technological Planning Project of China (No.20200403001SF)the National Key Research and Development Program of China (2021YFA1501800,2021YFA1501801,2021YFA1501802)。
文摘Rational design of catalytic sites to activate the C≡C bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by controlling the impregnation solutions. The π electrons flowing from acetylene to Cu site are facilitated over the electron-deficient Cu sites, achieving high activation of C≡C bond. The contradiction between the increased activation of acetylene required for enhanced catalytic activity and the resistance of Cu site to reduction by acetylene required for maintaining catalytic stability can be balanced by establishing strong interactions of Cu site with pyrrolic-N species. The catalytic activity displays a volcano shape scaling relationship as a function of Cu particle size. Tribasic copper chloride is concomitantly generated with the construction of electron-deficient Cu sites. The H–Cl bond of HCl can be activated over the tribasic copper chloride, accelerating the surface reaction of vinyl chloride production. This strategy of inducing electron deficiency provides new insight into the rational design of catalysts for the synthesis of vinyl chloride with a high catalytic performance.
基金the funding support from the National Natural Science Foundation of China(Nos.22202036 and 22302001)the Jilin Province Scientific,the Technological Planning Project of China(No.20230101292JC).
文摘In this study,a novel non-metallic carbon-based catalyst co-doped with boron and nitrogen(B,N)was successfully synthesized.By precisely controlling the carbonization temperature of a binary mixed ionic liquid,we selectively modified the doping site structure,ultimately constructing a B,N co-doped frustrated Lewis acid-base pair catalyst.This catalyst exhibited remarkable catalytic activity,selectivity,and stability in the dehydrochlorination reaction of 1,1,2-trichloroethane(TCE).Detailed characterization and theoretical calculations revealed that the primary active center of this catalyst was the BN_(3)configuration.Compared to conventional graphitic N structures,the BN_(3)structure had a higher p-band center,ensuring superior adsorption and activation capabilities for TCE during the reaction.Within the BN_(3)site,three negatively charged nitrogen atoms acted as Lewis bases,while positively charged boron atoms acted as Lewis acids.This synergistic interaction facilitated the specific dissociation of chlorine and hydrogen atoms from TCE,significantly enhancing the 1,1-dichloroethene selectivity.Through this research,we not only explored the active site structure and catalytic mechanism of B,N co-doped catalysts in depth but also provided an efficient,selective,and stable catalyst for the dehydrochlorination of TCE,contributing significantly to the development of non-metallic catalysts.
基金the National Key Research and Development Program of China(Nos.2021YFA1501800,2021YFA1501801,and 2021YFA1501802)the Science and Technology Department of Zhejiang Province(No.LGG20B060004)+1 种基金the Zhejiang Province Public Welfare Technology Application Research Project(No.LGF19B050002)the National Natural Science Foundation of China(Nos.21606199 and 21976129)are gratefully acknowledged.
文摘Semi-hydrogenation of acetylene is of growing interest and popularity but subjects to a major challenge in selective hydrogenation to ethylene.Here,we report a strategy that uses graphdiyne(GDY)as a carrier to prepare single-cluster catalysts(SCCs),which on average clusters composed of three atoms(denoted as Pd3 trimer)and applied it to the acetylene semihydrogenation in the presence of large amounts of ethylene.Based on experimental results and systematic quantum chemical research and computational screening,we found that there are multiple active Pd structures on GDY and the Pd3 trimer anchored on GDY is a specific and durable cluster with great potential for accurate and efficient heterogeneous catalysis.The synergetic effects between neighboring atoms in Pd trimer guarantee easy desorption of ethylene and the absence of unselective hydride species thereby preventing excessive hydrogenation to generate unwanted byproducts,which is a crucial mechanism for the excellent selectivity of the catalyst.This new method for precise synthesis Pd clusters provides accurate ways for designing selective hydrogenation catalysts at the atomic scale.
基金funds from National Natural Science Foundation of China(81372536 to S.W.,81502452 to X.C.and 81602485 to Y.Z.).
文摘Dendritic cell(DC)tumor vaccines exert their antitumor effects through the induction of effector T cells.We recently identified Tc9 cells as a new potent antitumor effector T cell subset.However,approaches to direct DCs to preferably prime antitumor Tc9 cells should be further exploited.Here,we demonstrate that the addition of interleukin(IL)-33 potently promotes the induction of Tc9 cells by DCs in vitro and in vivo.IL-33 treatment also drives the cytotoxic activities of DC-induced Tc9 cells.Notably,IL-33 treatment enhances cell survival and proliferation of DC-primed CD8+T cells.More importantly,the addition of IL-33 during in vitro priming of tumor-specific Tc9 cells by DCs increases the antitumor capability of Tc9 cells.Mechanistic studies demonstrated that IL-33 treatment inhibits exhaustive CD8+T cell differentiation by inhibiting PD-1 and 2B4 expression and increasing IL-2 and CD127(IL-7 receptor-α,IL-7Rα)expression in CD8+T cells.Finally,the addition of IL-33 further promotes the therapeutic efficacy of DC-based tumor vaccines in the OT-I mouse model.Our study demonstrates the important role of IL-33 in DC-induced Tc9 cell differentiation and antitumor immunity and may have important clinical implications.
基金Zhejiang Normal University for providing the financial support (YS304320035, YS304320036, ZZ323205020521005039)Financial support from the National Natural Science Foundation of China (NSFC, 21606199)+1 种基金the Science and Technology Department of Zhejiang Province (LGG20B060004)the National Key Research and Development Program of China (2021YFA1501800, 2021YFA1501801, 2021YFA1501802) are also gratefully acknowledged。
文摘A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.
基金the National Natural Science Foundation of China(NSFCgrant No.21606199,21476207)the Science and Technology Department of Zhejiang Province(LGG20B060004)are gratefully acknowledged.
文摘In the process of acetylene hydrochlorination,the rapid deactivation of supported gold(Au)catalysts by acetylene is still a huge challenge.Here,we provide an innovative strategy for constructing an acetylene–deficient reaction phase on the active site by coating an ionic liquid film on the Au(H2O)/C surface.The reactant ratio of C2H2 to HCl in this acetylene–deficient reaction phase is 1:132,in contrast to the 1:1 M ratio in the gas phase,thus boosting the catalytic stability of Au(H2O)/C catalysts.The kinetic and theoretical analysis showed that the reduction of cationic gold by C2H2 and the generation of carbon deposition can be inhibited in this constructed reaction phase during reaction.The current work not only broadens the scope of supported Au catalysts in acetylene hydrochlorination,but also verifies the perspective of the tunability of stoichiometric balance,which can be used in other catalytic applications.
