To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study invest...To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.展开更多
Carbosilane dendrimers with p-bromophenyl core were synthesized by alternating Grignard and hydrosilylation reaction. And the α-naphthalenyl was connected to the core by the Suzuki coupling reaction. A new carbosilan...Carbosilane dendrimers with p-bromophenyl core were synthesized by alternating Grignard and hydrosilylation reaction. And the α-naphthalenyl was connected to the core by the Suzuki coupling reaction. A new carbosilane dendrimer with big π-conjugated structure [4-(naphthalen-l-yl)phenyl core] was given. It shows Suzuki coupling reaction is an effective and powerful core-functionalization method and the satisfactory result can be obtained through prolonging the reaction time with the increase of the generation of dendrimer.展开更多
The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols wit...The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols with high diasterepselectivities.展开更多
Herein, well-dispersed Palladium(Pd) nanoparticles(NPs) with good catalytic activities were prepared using a wood nanomaterial(WNM) as a reductant and a supporting agent. Various factors that influenced the NP morphol...Herein, well-dispersed Palladium(Pd) nanoparticles(NPs) with good catalytic activities were prepared using a wood nanomaterial(WNM) as a reductant and a supporting agent. Various factors that influenced the NP morphologies, including reaction time, temperature, and precursor concentration were studied. The as-prepared Pd NPs/WNM showed good catalytic performance for Suzuki coupling reactions.展开更多
In the case of Pd(PPh3)4 as catalyst and toluene as reaction solvent, the desired biaryls and polyaryls were synthesized in excellent yield and on a large scale.
Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium(0) complex. Thi...Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium(0) complex. This palladium complex can be easily recovered and reused many times without loss of activity.展开更多
Oxygen vacancy(Vo)is a significant component in defect engineering.The present work reports the anchoring effects of initial Vo for further loading modifications and the reducing capacity of photoinduced Vo for pure w...Oxygen vacancy(Vo)is a significant component in defect engineering.The present work reports the anchoring effects of initial Vo for further loading modifications and the reducing capacity of photoinduced Vo for pure water splitting.Herein,we propose Ni-loaded Cu-doped TiO_(2)(NCT)materials by successive doping and loading.The continuously added Ni ions should accumulate around the Vos and gradually grow into complete nickel oxide crystals,achieving a higher average valence state of the Ni species.NiO crystals can be detected on a 0.5%NCT sample,while the structure of Ni_(2)O_(3) has been confirmed with a higher nickel mass ratio.Moreover,the introduction of nickel oxide effectively improves the photochemical and electrochemical performance by the interface charge separation,finally reaching an H2 yield of 30.6 pmol/g-cat on 0.5%NCT for Vo-based photo-thermal coupling reaction,which consists of Vo generation in photo and Vo consumption in thermal environment.In situ infrared spectroscopy further indicated that the presence of high valence state nickel oxide hindered the H2 formation but effectively promoted the conventional oxidizing reaction,with an H2 yield of 20.6 mmol/g-cat in a methanol-water reaction on the 2.0%NCT material.In summary,Vo controls the morphological structure of Ni loading and produces diverse effects for reactions with dissimilar mechanisms,which provides a novel way to design modifications for promoting various chemical reactions.展开更多
篢he oxidative coupling reaction of isorhapontigenin using sliver oxide as oxidant afforded a major product, named shegansu B(2), which was isolated from the roots of Belamcanda chinensis (L.)DC. Both the natural ...篢he oxidative coupling reaction of isorhapontigenin using sliver oxide as oxidant afforded a major product, named shegansu B(2), which was isolated from the roots of Belamcanda chinensis (L.)DC. Both the natural and synthetic Shegansu B have the same potent antagonism activities of leukotriene B4,D4 receptor.展开更多
The reductive coupling reactions of aryl sulfonyl chloride induced by (TiCl4-Zn) reagent affords diaryl disulfide. However, reaction of aryl sulfonyl chloride with α,β-unsaturated ester under the same condition affo...The reductive coupling reactions of aryl sulfonyl chloride induced by (TiCl4-Zn) reagent affords diaryl disulfide. However, reaction of aryl sulfonyl chloride with α,β-unsaturated ester under the same condition affords β-arylsulfo ester.展开更多
The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geomet...The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geometries of the reactants,transition states, intermediates and products were optimized at the B3LYP/6-31+G* level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-311+G* level was individually investigated. Polarizable continuum models(PCM)were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3,does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the ratelimiting step is reduced by 56.53 kJ mol-1 in gas and 44.84 kJ mol 1in solvent, demonstrating a high catalytic efficiency of CuI.展开更多
The intramolecular reductive coupling reaction of 1,6-bis(subshtuted indolyl)hexane-1,6-dione using zero-valent titanium reagent as catalyst proderes the novel photochromic 1,2-diheterocyclic cyclohexenes 2, together ...The intramolecular reductive coupling reaction of 1,6-bis(subshtuted indolyl)hexane-1,6-dione using zero-valent titanium reagent as catalyst proderes the novel photochromic 1,2-diheterocyclic cyclohexenes 2, together with unexpected compounds 3展开更多
Polyanilines(PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as ...Polyanilines(PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as the support of nano metal catalysts. In comparison with inorganic supports, the nano metals on PANIs were firmly anchored via the coordination bond so that they are not easily to lose during the reaction process. Moreover, since PANIs are versatile materials and their chemical features can be adjusted by introducing functional groups onto the monomers, the catalytic activities of the prepared catalysts are tunable. During the past decade, PANIs-supported nano metal catalysts have been widely applied in a variety of coupling reactions. This review aims to summarize the recent advances and give a perspective.展开更多
Electrochemical C–N coupling has generated intense research interest as a promising approach to reduce carbon and nitrogen emissions and store excess renewable electricity in valuable chemicals(e.g.,urea,amides,and a...Electrochemical C–N coupling has generated intense research interest as a promising approach to reduce carbon and nitrogen emissions and store excess renewable electricity in valuable chemicals(e.g.,urea,amides,and amines).In this review,we discuss the emerging trends in electrocatalytic C–N coupling reactions using CO_(2) and inorganic nitrogenous species(i.e.,dinitrogen(N_(2))),nitrate(NO_(2)^(-)),nitrite(NO_(3)^(-)),and ammonia(NH_(3))as raw materials.The related reaction mechanisms and potential design principles for advanced electrocatalysts are outlined.In addition,the effects of different reactors,including H-cells,membrane-based flow reactors,and membrane electrode assembly electrolyzers,on the coupling reactions are emphasized.Finally,the current challenges and future opportunities in this field are described.We aim to provide an up-to-date overview of the electrochemical C–N coupling system to advance progress toward its practical application.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the...Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.展开更多
Due to the increasing demand for the sustainability of modern organic chemistry, the development of green and powerful methods for C-C and C-B bond formation is highly desired. Among them, the transition-metal-free co...Due to the increasing demand for the sustainability of modern organic chemistry, the development of green and powerful methods for C-C and C-B bond formation is highly desired. Among them, the transition-metal-free coupling reactions of gem–diborylalkanes emerge as one valuable tool for organic chemists in the last decade. The review covers selected representative examples. A comparison of these reactions with transition-metal-catalyzed reactions is provided. The recent example of α-boryl radical formation from gem–diborylalkanes is also briefly discussed.展开更多
Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this a...Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this article, an anthraquinone-based copper(I)cyclic trinuclear complex(1) was designed and it featured strong visible light absorption, high charge separation efficiency and photochemical properties. Complex 1 as a heterogeneous photocatalyst can efficiently catalyze homo-coupling of terminal alkynes and denitrification-oxidative coupling reaction between hydrazinopyridine and terminal alkynes with excellent yield(up to 99%), broad substrate tolerance(27 examples) and superior reusability(up to 10 cycles without loss of performance) under mild conditions.展开更多
基金jointly supported by the National Key Research and Development Program of China (2019YFC1905800)the National Key Research & Development Program of China (2018YFC1903500)+4 种基金the commercial project by Beijing Zhong Dian Hua Yuan Environment Protection Technology Co., Ltd. (E01211200005)the Regional key projects of the science and technology service network program (STS program) of the Chinese Academy of Sciences (KFJ-STS-QYZD-153)the Ningbo Science and Technology Innovation Key Projects (2020Z099, 2022Z028)the Ningbo Municipal Commonweal Key Program (2019C10033)the support of Mineral Resources Analytical and Testing Center, Institute of Process Engineering, Chinese Academy of Science
文摘To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.
文摘Carbosilane dendrimers with p-bromophenyl core were synthesized by alternating Grignard and hydrosilylation reaction. And the α-naphthalenyl was connected to the core by the Suzuki coupling reaction. A new carbosilane dendrimer with big π-conjugated structure [4-(naphthalen-l-yl)phenyl core] was given. It shows Suzuki coupling reaction is an effective and powerful core-functionalization method and the satisfactory result can be obtained through prolonging the reaction time with the increase of the generation of dendrimer.
文摘The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols with high diasterepselectivities.
基金supported by the Hebei Key Discipline Construction Project
文摘Herein, well-dispersed Palladium(Pd) nanoparticles(NPs) with good catalytic activities were prepared using a wood nanomaterial(WNM) as a reductant and a supporting agent. Various factors that influenced the NP morphologies, including reaction time, temperature, and precursor concentration were studied. The as-prepared Pd NPs/WNM showed good catalytic performance for Suzuki coupling reactions.
基金Support from the University of Science and Technology of China the National Natural Science Foundation of China are gratefully acknowledged (NO. 50073021).
文摘In the case of Pd(PPh3)4 as catalyst and toluene as reaction solvent, the desired biaryls and polyaryls were synthesized in excellent yield and on a large scale.
基金National Natural Science Foundation of China (Project 20462002) Natural Science Foundation of Jiangxi Province (Project 0420015) for financial support.
文摘Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium(0) complex. This palladium complex can be easily recovered and reused many times without loss of activity.
基金financially supported by the National Natural Science Foundation of China(51976190)the Zhejiang Provincial Natural Science Foundation(LR18E060001)+1 种基金the Innovative Research Groups of the National Natural Science Foundation of China(51621005)the Fundamental Research Funds for the Central Universities(2019FZA4013)。
文摘Oxygen vacancy(Vo)is a significant component in defect engineering.The present work reports the anchoring effects of initial Vo for further loading modifications and the reducing capacity of photoinduced Vo for pure water splitting.Herein,we propose Ni-loaded Cu-doped TiO_(2)(NCT)materials by successive doping and loading.The continuously added Ni ions should accumulate around the Vos and gradually grow into complete nickel oxide crystals,achieving a higher average valence state of the Ni species.NiO crystals can be detected on a 0.5%NCT sample,while the structure of Ni_(2)O_(3) has been confirmed with a higher nickel mass ratio.Moreover,the introduction of nickel oxide effectively improves the photochemical and electrochemical performance by the interface charge separation,finally reaching an H2 yield of 30.6 pmol/g-cat on 0.5%NCT for Vo-based photo-thermal coupling reaction,which consists of Vo generation in photo and Vo consumption in thermal environment.In situ infrared spectroscopy further indicated that the presence of high valence state nickel oxide hindered the H2 formation but effectively promoted the conventional oxidizing reaction,with an H2 yield of 20.6 mmol/g-cat in a methanol-water reaction on the 2.0%NCT material.In summary,Vo controls the morphological structure of Ni loading and produces diverse effects for reactions with dissimilar mechanisms,which provides a novel way to design modifications for promoting various chemical reactions.
文摘篢he oxidative coupling reaction of isorhapontigenin using sliver oxide as oxidant afforded a major product, named shegansu B(2), which was isolated from the roots of Belamcanda chinensis (L.)DC. Both the natural and synthetic Shegansu B have the same potent antagonism activities of leukotriene B4,D4 receptor.
文摘The reductive coupling reactions of aryl sulfonyl chloride induced by (TiCl4-Zn) reagent affords diaryl disulfide. However, reaction of aryl sulfonyl chloride with α,β-unsaturated ester under the same condition affords β-arylsulfo ester.
文摘The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geometries of the reactants,transition states, intermediates and products were optimized at the B3LYP/6-31+G* level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-311+G* level was individually investigated. Polarizable continuum models(PCM)were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3,does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the ratelimiting step is reduced by 56.53 kJ mol-1 in gas and 44.84 kJ mol 1in solvent, demonstrating a high catalytic efficiency of CuI.
文摘The intramolecular reductive coupling reaction of 1,6-bis(subshtuted indolyl)hexane-1,6-dione using zero-valent titanium reagent as catalyst proderes the novel photochromic 1,2-diheterocyclic cyclohexenes 2, together with unexpected compounds 3
基金the financial support by the Open Fund Project of Hubei Key Laboratory of Radiation Chemistry and Functional Materials (No. 2021KF07)the Research and Development Fund Project of Hubei University of Science and Technology (Nos. 2021ZX13, H2019004)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Polyanilines(PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as the support of nano metal catalysts. In comparison with inorganic supports, the nano metals on PANIs were firmly anchored via the coordination bond so that they are not easily to lose during the reaction process. Moreover, since PANIs are versatile materials and their chemical features can be adjusted by introducing functional groups onto the monomers, the catalytic activities of the prepared catalysts are tunable. During the past decade, PANIs-supported nano metal catalysts have been widely applied in a variety of coupling reactions. This review aims to summarize the recent advances and give a perspective.
基金This work was financially supported in part by the National Key R&D Program of China(2020YFA0406103)NSFC(21725102,22122506,91961106,U1832156,22105192,22075267)+4 种基金Strategic Priority Research Program of the CAS(XDPB14)the Open Funding Project of National Key Laboratory of Human Factors Engineering(SYFD062010K)Anhui Provincial Natural Science Foundation(2008085J05)Youth Innovation Promotion Association of CAS(2019444)China Post-doctoral Science Foundation(2021M693065,2021TQ0322).
文摘Electrochemical C–N coupling has generated intense research interest as a promising approach to reduce carbon and nitrogen emissions and store excess renewable electricity in valuable chemicals(e.g.,urea,amides,and amines).In this review,we discuss the emerging trends in electrocatalytic C–N coupling reactions using CO_(2) and inorganic nitrogenous species(i.e.,dinitrogen(N_(2))),nitrate(NO_(2)^(-)),nitrite(NO_(3)^(-)),and ammonia(NH_(3))as raw materials.The related reaction mechanisms and potential design principles for advanced electrocatalysts are outlined.In addition,the effects of different reactors,including H-cells,membrane-based flow reactors,and membrane electrode assembly electrolyzers,on the coupling reactions are emphasized.Finally,the current challenges and future opportunities in this field are described.We aim to provide an up-to-date overview of the electrochemical C–N coupling system to advance progress toward its practical application.
基金financially supported by the National Natural Science Foundation of China(22002084,22072081)the China Postdoctoral Science Foundation(2020M683420)+1 种基金the Fundamental Research Funds for the Central Universities(GK202103111)the 111 Project(B21005)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.
基金financial support from the National Natural Science Foundation of China (No. 22101261)。
文摘Due to the increasing demand for the sustainability of modern organic chemistry, the development of green and powerful methods for C-C and C-B bond formation is highly desired. Among them, the transition-metal-free coupling reactions of gem–diborylalkanes emerge as one valuable tool for organic chemists in the last decade. The review covers selected representative examples. A comparison of these reactions with transition-metal-catalyzed reactions is provided. The recent example of α-boryl radical formation from gem–diborylalkanes is also briefly discussed.
基金Guo-Hong Ning is thankful for the support from the Guangdong Basic and Applied Basic Research Foundation (2019B151502024)the Guangzhou Science and Technology Project (202201020038)+1 种基金supported by the National Natural Science Foundation of China (22371091, 21975104, 22150004, 22101099)the Guangdong Major Project of Basic and Applied Research (2019B030302009)。
文摘Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this article, an anthraquinone-based copper(I)cyclic trinuclear complex(1) was designed and it featured strong visible light absorption, high charge separation efficiency and photochemical properties. Complex 1 as a heterogeneous photocatalyst can efficiently catalyze homo-coupling of terminal alkynes and denitrification-oxidative coupling reaction between hydrazinopyridine and terminal alkynes with excellent yield(up to 99%), broad substrate tolerance(27 examples) and superior reusability(up to 10 cycles without loss of performance) under mild conditions.