To minimize the loading level of the char-forming phosphorus based flame retardants in the poly（lactic acid） （PLA） with reduced flammability, we have developed the flame-retarded PLA nanocomposites by melt blendin...To minimize the loading level of the char-forming phosphorus based flame retardants in the poly（lactic acid） （PLA） with reduced flammability, we have developed the flame-retarded PLA nanocomposites by melt blending method incorporating organically modified montmorillonite （OMMT） and aluminium diethylphosphinate （A1Pi） additives. The influence of A1Pi and OMMT on flame retardancy and thermal stability of PLA was thoroughly investigated by means of the limiting oxygen index （LOI）, UL94 test, cone calorimeter, X-ray diffraction （XRD）, thermogravimetric analysis and scanning electronic microscopy （SEM）. The experimental results show that the PLA/A1Pi/OMMT system has excellent fire retardancy. The LOI value increases from 19% for pristine PLA to 28% for the flame-retarded PLA. Cone calorimeter analysis of the PLA/A1Pi/OMMT exhibits a reduction in the peak heat release rate values by 26.2%. Thermogravimetric analysis and SEM of cone calorimeter residues indicate that OMMT significantly enhances the thermal stability, promotes char-forming and suppresses the melt dripping. The research of this study implies that the combining of the flame retardant and organoclay results in a synergistic effect. In addition, the flame-retarded PLA nanocomposite also exhibits notable increase in the impact strength and the elongation at break.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
The chemo-,regio-,and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge.In this study,a Pd-catalyzed hydrofunctionalization is developed fo...The chemo-,regio-,and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge.In this study,a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes.Notably,this methodology is suitable for both phosphine oxide and phosphinate nucleophiles,providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.展开更多
Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical p...Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.展开更多
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the ...Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy,mild reaction conditions and simplicity of operation.Allenolates,Morita−Baylis−Hillman(MBH)alcohols and their derivatives(MBHADs),electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations,which formed many phosphonium species such asβ-phosphonium enolates,β-phosphonium dienolates and vinyl phosphonium ylides as intermediates.This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations.Thus,a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates,MBH alcohols and MBHADs,electron-deficient olefins and alkynes are presented in Chapters 2-6,respectively.展开更多
A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively m...A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions.Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities(35 examples,up to>99%ee).展开更多
The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic...The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.展开更多
Rh/SiO2 catalysts with tethered-phosphines with different alkyl spacer lengths have been prepared,tested and characterized.Lengthening the alkyl spacer of the tethered-phosphine improved the flexibility of tethered-ph...Rh/SiO2 catalysts with tethered-phosphines with different alkyl spacer lengths have been prepared,tested and characterized.Lengthening the alkyl spacer of the tethered-phosphine improved the flexibility of tethered-phospine,promoted the formation of active species and enhanced the activity of hydroformylation over other tethered-phosphine modified Rh/SiO2 catalysts.展开更多
The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an...The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.展开更多
[Objective] This study aimed to investigate the killing effect of mixed fumi- gation of phosphine and carbon dioxide on eggs of Lasioderma serricorne F. [Method] The outside-storage phosphine generator was placed in a...[Objective] This study aimed to investigate the killing effect of mixed fumi- gation of phosphine and carbon dioxide on eggs of Lasioderma serricorne F. [Method] The outside-storage phosphine generator was placed in a tabernacled smoke box, and the mortality rates of L. serricome F. eggs in the smoke box under conditions of different aluminium phosphide usage amount and different fumigation time were studied. In addition, the times needed by tabernacle and smoke box cen- ter to reach the phosphine concentration peak were recorded. [Result] The optimum conditions for killing the eggs of L. serricorne were as follows： temperature of （27± 2） ℃, relatively humidity of （45±5）%, aluminium phosphide usage amount of 1.5 g/m3 and effective exposure time of 96 h. The killing effect of mixed fumigation of phos- phine and carbon dioxide was increased with the extension of fumigation time. The increased usage amount of aluminium phosphide showed no significant effect on killing effect. The tabernacle space and smoke box center all required relatively short time to reach the phosphine concentration peak. If the tabernacle had a good airtightness, the overall fumigation time could be shortened. [Conclusion] The fumi- gation method is reliable, and it can be used for the control of L. serricorne F. in tobacco storage.展开更多
[Objective] This study aimed to investigate the effects of phosphine on germination and physiological characteristics of rice seeds. [Method] Simulation envi- ronments were conducted to study the effects of high-level...[Objective] This study aimed to investigate the effects of phosphine on germination and physiological characteristics of rice seeds. [Method] Simulation envi- ronments were conducted to study the effects of high-level phosphine on germination status and physiological characteristics of rice seeds and explore the early environ- mental and ecological effects of phosphine on rice growth in phosphorus cycle of paddy field. [Result] Experimental results showed that the increase of phosphine con- centration in the environment resulted in the decrease of germination rate and ger- mination potential by 11.11% and 19.71%, respectively. In addition, the activities of catalase （CAT） and peroxidase （POD） were reduced to 94.35% and 92.61%, respec- tively; the content of malondialdehyde （MDA） was maximally increased by 29.11%, indicating that both germination potential and growth condition of rice seeds were in- hibited under conditions of high-level phosphine. [Conclusion] This study provided theoretical basis for investigating the effects of phosphine on germination of rice seeds under natural environment.展开更多
We prepared a kind of metal oxide-modified walnut-shell activated carbon(MWAC) by KOH chemical activation method and used for PH_3 adsorption removal. Meanwhile, the PH_3 adsorption equilibrium was investigated experi...We prepared a kind of metal oxide-modified walnut-shell activated carbon(MWAC) by KOH chemical activation method and used for PH_3 adsorption removal. Meanwhile, the PH_3 adsorption equilibrium was investigated experimentally and fitted by the Toth equation, and the isosteric heat of PH_3 adsorption was calculated by the Clausius-Clapeyron Equation. The exhausted MWAC was regenerated by water washing and air drying. Moreover, the properties of five different samples were characterized by N_2 adsorption isotherm, SEM/EDS, XPS, and FTIR. The results showed that the maximum PH_3 equilibrium adsorption capacity was 595.56 mg/g. The MWAC had an energetically heterogeneous surface due to values of isosteric heat of adsorption ranging from 43 to 90 kJ/mol. The regeneration method provided an effective way for both adsorption species recycling and exhausted carbon regeneration. The high removal efficiency and big equilibrium adsorption capacity for PH_3 adsorption on the MWAC were related to its large surface area and high oxidation activity in PH_3 adsorption-oxidation to H_3 PO_4 and P_2 O_5. Furthermore, a possible PH_3 adsorption mechanism was proposed.展开更多
A new ternary Fe-based alloy catalyst FeCuP applied to decompose PH3 was prepared with low-cost material by chemical reduction deposition method. The properties of it were characterized by XRD, ICP and SEM. Its cataly...A new ternary Fe-based alloy catalyst FeCuP applied to decompose PH3 was prepared with low-cost material by chemical reduction deposition method. The properties of it were characterized by XRD, ICP and SEM. Its catalytic activity on the decomposition of PH3 and the decomposition conditions were studied. FeCuP alloy exhibits high thermal stabilities and high catalytic activity. Using it as catalyst, the decomposition temperature of phosphine decreases from over 800℃ to 400-500 ℃. The decomposition rate of phosphine achieved 100%.展开更多
The influence of tetracycline（TC） antibiotics on phosphine（PH3） production in the anaerobic wastewater treatment was studied. A lab-scale anaerobic baffled reactor with three compartments was employed to simulate ...The influence of tetracycline（TC） antibiotics on phosphine（PH3） production in the anaerobic wastewater treatment was studied. A lab-scale anaerobic baffled reactor with three compartments was employed to simulate this process. The reactor was operated in a TC-absence wastewater and 250 μg/L TC-presence wastewater for three months after a start-up period,respectively. The responses of p H, oxidation–reduction potential（ORP）, chemical oxygen demand（COD）, total phosphorus（TP）, enzymes activity（dehydrogenase and acid phosphatase）,and microbial community were investigated to reveal the effect of TC on PH3 production.Results suggested that the dehydrogenase（DH） activity, acid phosphatase（ACP） activity and COD have positive relationship with PH3 production, while p H, ORP level and the TP in liquid phase have negative relationship with PH3 production. With prolonged TC exposure, decrease in p H and increase in DH activity are beneficial to PH3 production, while decrease in COD and ACP activity are not the limiting factors for PH3 production.展开更多
A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tai...A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tail gas. N2 adsorption isotherm and X-ray diffrac-tion (XRD) results suggested that the addition of Zn could increase the adsorbent ultramicropores, decrease the adsorbent supermicropores and the adsorbent average pore diameter. Therefore it enhanced the PH3 adsorption capacity. Appropriate amoun...展开更多
Phosphine is a part of an atmospheric link of phosphorus cycle on earth, which could be an important pathway for phosphorus transport in environment. Wetland ecosystems are important locations for global biogeochemica...Phosphine is a part of an atmospheric link of phosphorus cycle on earth, which could be an important pathway for phosphorus transport in environment. Wetland ecosystems are important locations for global biogeochemical phosphorus cycle. In this study, production and emission fluxes of free phosphine from four wetlands types in southern China were observed in different seasons. The results showed that the concentration of phosphine liberated from wetlands was at pg/m^3·ng/m^3 level. The emission concentrations of different wetlands followed the sequence： paddy field （51.83 ± 3.06） ng/m^3 〉/marsh （46.54 ± 20.55） ng/m^3 〉 lake （37.05 ± 22.74） ng/m^3 〉〉 coastal wetland （1.71 ± 0.73） ng/m^3, the positive phosphine emission flux occurred in rice paddy field （6.67 ± 5.18） ng/（m^2.hr） and marsh （6.23 ± 26.9） ng/（m^2.hr）, while a negative phosphine flux of （-13.11 ± 35.04） ng/（m^2.hr） was observed on the water-air interface of Lake Taihu, suggesting that paddy field and marsh may be important sources for phosphine gas in atmosphere, while lake may be a sink of atmospheric phosphine gas during the sampling period. Atmospheric phosphine levels and emission flux from Yancheng marsh and rice paddy field varied in different seasons and vegetational zones. Both diffusion resistance in aqueous phase and temperature were dominating factors for the production and transportation of phosphine to atmosphere.展开更多
Phosphine(PH3) is a highly toxic air pollutant,commonly produced in phosphorous chemical industry.But it has received less research attention due to its handling difficultly.CO is the main content of the phosphorous c...Phosphine(PH3) is a highly toxic air pollutant,commonly produced in phosphorous chemical industry.But it has received less research attention due to its handling difficultly.CO is the main content of the phosphorous chemical industry tail gas,the concentration of which is always more than 80 vol.%,and it can be the feed gas to produce various valuable products such as formate,oxalate,and methanol and so on.But,PH3 is one of the important barriers,which is harmful to the following chemical process.In order to make use of the tail gas,PH3 should be removed firstly,and CO should be covered in the whole purified procedure at the same time.In this work,the modified activated carbon(MAC) was used as the adsorbent to separate PH3 from the mixture tail gas.Series of MAC adsorbents were prepared for the adsorption of PH3,which loaded Cu-Fe and Ce(La),or separately.The PH3 adsorption capacities,chemical and physical properties of MAC were all investigated.The results showed that over 99% PH3 adsorption efficiency was achieved when used MAC adsorbents.The removal efficiency and PH3 adsorption capacity of the Cu-Fe-Ce/AC(20:1:0.4) were both much higher than those modified activated carbons.The maximum PH3 adsorption capacity was 71 mg of PH3/g of MAC on the Cu-Fe-Ce/AC,which were much higher than literature data using CuO only for adsorbing hydride gases.展开更多
Matrix-bound phosphine （MBP） is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. Antarctic seabird guanos and ornith...Matrix-bound phosphine （MBP） is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. Antarctic seabird guanos and ornithogenic soils were used as materials to compare the different digestion methods for transforming matrix-bound phosphine into phosphine gas. The results demonstrated that more phosphine gas in most of Antarctic environmental materials was formed of matrix-bound phosphine by caustic digestion than by acidic digestion. The comparative study on different digestion methods also revealed that the fraction of MBP converted to gaseous phosphine during the digestion depended on the temperature. The optimal digestion temperature was close to 70℃and the optimal digestion time was about 20 min. Acidic conditions were more favorable for the release of matrix-bound phosphine compared to the neutral conditions. A proper water dilution can increase the production and emission of phosphine from the Antarctic penguin guanos.展开更多
New flame-retardant polyimide-silver nanocomposite containing phosphine oxide moiety in the main chain was synthesized by a convenient ultraviolet irradiation technique.A precursor such as AgNO_3 was used as the sourc...New flame-retardant polyimide-silver nanocomposite containing phosphine oxide moiety in the main chain was synthesized by a convenient ultraviolet irradiation technique.A precursor such as AgNO_3 was used as the source of the silver particles.Polyimide 6 as a source of polymer was synthesized by polycondensation reaction of bis（3-aminophenyl） phenyl phosphine oxide 4 with pyromellitic anhydride 5 in the presence of iso-quinoline as base and in m-cresol solution.The resulting composite film was characterized by FTIR spectroscopy,X-ray diffraction（XRD）,transmission electron microscopy（TEM）,thermogravimetry（TGA） and differential scanning calorimetry（DSC）.The average size of the nanometer Ag particles is about 10 nm.The temperature of 5 and 10%weight loss and also the char yield at 600℃of polyimide-silver nanocomposite 6a were higher than the pure PI 6.展开更多
A new 2-D variational method is proposed to calculate the vibrational energy levels of the symmetric P-H stretching vibration （vl） and the symmetric umbrella vibration （inversion vibration） （v2） of PH3^＋（^～X...A new 2-D variational method is proposed to calculate the vibrational energy levels of the symmetric P-H stretching vibration （vl） and the symmetric umbrella vibration （inversion vibration） （v2） of PH3^＋（^～X^2A″2） that has the tunneling effect. Because the symmetric internal Cartesian coordinates were employed in the calculations, the kinetic energy operator is very simple and the inversion vibrational mode is well characterized. In comparison with the often used I-D model to calculate the inversion vibrational energy levels, this 2-D method does not require an assmnption of reduced mass, and the interactions between the vl and v2 vibrational modes are taken into consideration. The calculated vibrational energy levels of PH3^＋ are the first reported 2-D calculation, and the average deviation to the experimental data is less than 3 cm^-1 for the first seven inversion vibrational energy levels. This method has also been applied to calculate the vibrational energy levels of NH3. The application to NH3 is less successful, which shows some limitations of the method compared with a full dimension computation.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51203118)the Shanghai Automotive Industry Science and Technology Development Foundation(No.1006)
文摘To minimize the loading level of the char-forming phosphorus based flame retardants in the poly（lactic acid） （PLA） with reduced flammability, we have developed the flame-retarded PLA nanocomposites by melt blending method incorporating organically modified montmorillonite （OMMT） and aluminium diethylphosphinate （A1Pi） additives. The influence of A1Pi and OMMT on flame retardancy and thermal stability of PLA was thoroughly investigated by means of the limiting oxygen index （LOI）, UL94 test, cone calorimeter, X-ray diffraction （XRD）, thermogravimetric analysis and scanning electronic microscopy （SEM）. The experimental results show that the PLA/A1Pi/OMMT system has excellent fire retardancy. The LOI value increases from 19% for pristine PLA to 28% for the flame-retarded PLA. Cone calorimeter analysis of the PLA/A1Pi/OMMT exhibits a reduction in the peak heat release rate values by 26.2%. Thermogravimetric analysis and SEM of cone calorimeter residues indicate that OMMT significantly enhances the thermal stability, promotes char-forming and suppresses the melt dripping. The research of this study implies that the combining of the flame retardant and organoclay results in a synergistic effect. In addition, the flame-retarded PLA nanocomposite also exhibits notable increase in the impact strength and the elongation at break.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
基金the National Natural Science Foundation of China(NSFC,No.22271241),Yunnan Key Laboratory of Chiral Functional Substance Research and Application(No.202402AN360010)Research Grants Council of Hong Kong(GRF,No.12303422)HKBU KRPS grant for financial support.
文摘The chemo-,regio-,and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge.In this study,a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes.Notably,this methodology is suitable for both phosphine oxide and phosphinate nucleophiles,providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
文摘Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.
基金the National Natural Science Foundation of China(Nos.22171147 and 21871148)for the financial support。
文摘Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy,mild reaction conditions and simplicity of operation.Allenolates,Morita−Baylis−Hillman(MBH)alcohols and their derivatives(MBHADs),electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations,which formed many phosphonium species such asβ-phosphonium enolates,β-phosphonium dienolates and vinyl phosphonium ylides as intermediates.This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations.Thus,a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates,MBH alcohols and MBHADs,electron-deficient olefins and alkynes are presented in Chapters 2-6,respectively.
基金the financial support of the National Natural Science Foundation of China(No.21672133)the Opening Foundation of Key Laboratory of Applied Surface and Colloid Chemistry,Ministry of Education(No.GK202205011)the Fundamental Research Funds for the Central Universities(Nos.GK202307007 and GK202002003)。
文摘A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions.Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities(35 examples,up to>99%ee).
文摘The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.
基金financially supported by the National Natural Science Foundation of China(21273227,20903090)~~
文摘Rh/SiO2 catalysts with tethered-phosphines with different alkyl spacer lengths have been prepared,tested and characterized.Lengthening the alkyl spacer of the tethered-phosphine improved the flexibility of tethered-phospine,promoted the formation of active species and enhanced the activity of hydroformylation over other tethered-phosphine modified Rh/SiO2 catalysts.
基金supported by the National Natural Science Foundation of China(21473058,21273077)~~
文摘The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.
文摘[Objective] This study aimed to investigate the killing effect of mixed fumi- gation of phosphine and carbon dioxide on eggs of Lasioderma serricorne F. [Method] The outside-storage phosphine generator was placed in a tabernacled smoke box, and the mortality rates of L. serricome F. eggs in the smoke box under conditions of different aluminium phosphide usage amount and different fumigation time were studied. In addition, the times needed by tabernacle and smoke box cen- ter to reach the phosphine concentration peak were recorded. [Result] The optimum conditions for killing the eggs of L. serricorne were as follows： temperature of （27± 2） ℃, relatively humidity of （45±5）%, aluminium phosphide usage amount of 1.5 g/m3 and effective exposure time of 96 h. The killing effect of mixed fumigation of phos- phine and carbon dioxide was increased with the extension of fumigation time. The increased usage amount of aluminium phosphide showed no significant effect on killing effect. The tabernacle space and smoke box center all required relatively short time to reach the phosphine concentration peak. If the tabernacle had a good airtightness, the overall fumigation time could be shortened. [Conclusion] The fumi- gation method is reliable, and it can be used for the control of L. serricorne F. in tobacco storage.
基金Supported by National Natural Science Foundation of China(41071305)~~
文摘[Objective] This study aimed to investigate the effects of phosphine on germination and physiological characteristics of rice seeds. [Method] Simulation envi- ronments were conducted to study the effects of high-level phosphine on germination status and physiological characteristics of rice seeds and explore the early environ- mental and ecological effects of phosphine on rice growth in phosphorus cycle of paddy field. [Result] Experimental results showed that the increase of phosphine con- centration in the environment resulted in the decrease of germination rate and ger- mination potential by 11.11% and 19.71%, respectively. In addition, the activities of catalase （CAT） and peroxidase （POD） were reduced to 94.35% and 92.61%, respec- tively; the content of malondialdehyde （MDA） was maximally increased by 29.11%, indicating that both germination potential and growth condition of rice seeds were in- hibited under conditions of high-level phosphine. [Conclusion] This study provided theoretical basis for investigating the effects of phosphine on germination of rice seeds under natural environment.
基金Funded by the National Natural Science Foundation of China(51566017)
文摘We prepared a kind of metal oxide-modified walnut-shell activated carbon(MWAC) by KOH chemical activation method and used for PH_3 adsorption removal. Meanwhile, the PH_3 adsorption equilibrium was investigated experimentally and fitted by the Toth equation, and the isosteric heat of PH_3 adsorption was calculated by the Clausius-Clapeyron Equation. The exhausted MWAC was regenerated by water washing and air drying. Moreover, the properties of five different samples were characterized by N_2 adsorption isotherm, SEM/EDS, XPS, and FTIR. The results showed that the maximum PH_3 equilibrium adsorption capacity was 595.56 mg/g. The MWAC had an energetically heterogeneous surface due to values of isosteric heat of adsorption ranging from 43 to 90 kJ/mol. The regeneration method provided an effective way for both adsorption species recycling and exhausted carbon regeneration. The high removal efficiency and big equilibrium adsorption capacity for PH_3 adsorption on the MWAC were related to its large surface area and high oxidation activity in PH_3 adsorption-oxidation to H_3 PO_4 and P_2 O_5. Furthermore, a possible PH_3 adsorption mechanism was proposed.
基金supported by the Tianjin Natural Science Foundation(No.043801311).
文摘A new ternary Fe-based alloy catalyst FeCuP applied to decompose PH3 was prepared with low-cost material by chemical reduction deposition method. The properties of it were characterized by XRD, ICP and SEM. Its catalytic activity on the decomposition of PH3 and the decomposition conditions were studied. FeCuP alloy exhibits high thermal stabilities and high catalytic activity. Using it as catalyst, the decomposition temperature of phosphine decreases from over 800℃ to 400-500 ℃. The decomposition rate of phosphine achieved 100%.
基金supported by the State Key Laboratory of Pollution Control and Resource Reuse(No.PCRRF14006)the State Key Laboratory of Lake Science and Environment(No.2016SKL011)+1 种基金the Student Research Project of South China University of Technology(2016)the Shenzhen Municipal Science and Technology Innovation Committee through project Shenzhen Key Laboratory of Soil and Groundwater Pollution Control(No.ZDSY20150831141712549)
文摘The influence of tetracycline（TC） antibiotics on phosphine（PH3） production in the anaerobic wastewater treatment was studied. A lab-scale anaerobic baffled reactor with three compartments was employed to simulate this process. The reactor was operated in a TC-absence wastewater and 250 μg/L TC-presence wastewater for three months after a start-up period,respectively. The responses of p H, oxidation–reduction potential（ORP）, chemical oxygen demand（COD）, total phosphorus（TP）, enzymes activity（dehydrogenase and acid phosphatase）,and microbial community were investigated to reveal the effect of TC on PH3 production.Results suggested that the dehydrogenase（DH） activity, acid phosphatase（ACP） activity and COD have positive relationship with PH3 production, while p H, ORP level and the TP in liquid phase have negative relationship with PH3 production. With prolonged TC exposure, decrease in p H and increase in DH activity are beneficial to PH3 production, while decrease in COD and ACP activity are not the limiting factors for PH3 production.
基金Project supported by the Key Program of National High Technology Research and Development Program of China (863 Program) (2008AA062602)the Young and Middle-aged Academic and Technical Back-up Personnel Program of Yunnan Province (2007PY01-10)the Analysis and Measurement Foundation of Kunming University of Science & Technology
文摘A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tail gas. N2 adsorption isotherm and X-ray diffrac-tion (XRD) results suggested that the addition of Zn could increase the adsorbent ultramicropores, decrease the adsorbent supermicropores and the adsorbent average pore diameter. Therefore it enhanced the PH3 adsorption capacity. Appropriate amoun...
基金supported by the National Basic Research Program (973) of China (No. 2008CB418003)the Jiangsu Natural Science Foundation (No. BK2008276)+2 种基金the National Natural Science Foundation of China (No.21077051, 30700020)the International Foundation of Science (No. A/4425-1)the Self-Research Subject of State Key Laboratory of Pollution Control and Resource Reuse
文摘Phosphine is a part of an atmospheric link of phosphorus cycle on earth, which could be an important pathway for phosphorus transport in environment. Wetland ecosystems are important locations for global biogeochemical phosphorus cycle. In this study, production and emission fluxes of free phosphine from four wetlands types in southern China were observed in different seasons. The results showed that the concentration of phosphine liberated from wetlands was at pg/m^3·ng/m^3 level. The emission concentrations of different wetlands followed the sequence： paddy field （51.83 ± 3.06） ng/m^3 〉/marsh （46.54 ± 20.55） ng/m^3 〉 lake （37.05 ± 22.74） ng/m^3 〉〉 coastal wetland （1.71 ± 0.73） ng/m^3, the positive phosphine emission flux occurred in rice paddy field （6.67 ± 5.18） ng/（m^2.hr） and marsh （6.23 ± 26.9） ng/（m^2.hr）, while a negative phosphine flux of （-13.11 ± 35.04） ng/（m^2.hr） was observed on the water-air interface of Lake Taihu, suggesting that paddy field and marsh may be important sources for phosphine gas in atmosphere, while lake may be a sink of atmospheric phosphine gas during the sampling period. Atmospheric phosphine levels and emission flux from Yancheng marsh and rice paddy field varied in different seasons and vegetational zones. Both diffusion resistance in aqueous phase and temperature were dominating factors for the production and transportation of phosphine to atmosphere.
基金Project supported by the Key Program of National High Technology Research and Development Program of China (863 Program) (2008AA062602)the Young and Middle-aged Academic and Technical Back-up Personnel Program of Yunnan Province (2007PY01-10)
文摘Phosphine(PH3) is a highly toxic air pollutant,commonly produced in phosphorous chemical industry.But it has received less research attention due to its handling difficultly.CO is the main content of the phosphorous chemical industry tail gas,the concentration of which is always more than 80 vol.%,and it can be the feed gas to produce various valuable products such as formate,oxalate,and methanol and so on.But,PH3 is one of the important barriers,which is harmful to the following chemical process.In order to make use of the tail gas,PH3 should be removed firstly,and CO should be covered in the whole purified procedure at the same time.In this work,the modified activated carbon(MAC) was used as the adsorbent to separate PH3 from the mixture tail gas.Series of MAC adsorbents were prepared for the adsorption of PH3,which loaded Cu-Fe and Ce(La),or separately.The PH3 adsorption capacities,chemical and physical properties of MAC were all investigated.The results showed that over 99% PH3 adsorption efficiency was achieved when used MAC adsorbents.The removal efficiency and PH3 adsorption capacity of the Cu-Fe-Ce/AC(20:1:0.4) were both much higher than those modified activated carbons.The maximum PH3 adsorption capacity was 71 mg of PH3/g of MAC on the Cu-Fe-Ce/AC,which were much higher than literature data using CuO only for adsorbing hydride gases.
基金supported by the National Natural Sci-ence Foundation of China (No. 40676005)
文摘Matrix-bound phosphine （MBP） is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. Antarctic seabird guanos and ornithogenic soils were used as materials to compare the different digestion methods for transforming matrix-bound phosphine into phosphine gas. The results demonstrated that more phosphine gas in most of Antarctic environmental materials was formed of matrix-bound phosphine by caustic digestion than by acidic digestion. The comparative study on different digestion methods also revealed that the fraction of MBP converted to gaseous phosphine during the digestion depended on the temperature. The optimal digestion temperature was close to 70℃and the optimal digestion time was about 20 min. Acidic conditions were more favorable for the release of matrix-bound phosphine compared to the neutral conditions. A proper water dilution can increase the production and emission of phosphine from the Antarctic penguin guanos.
文摘New flame-retardant polyimide-silver nanocomposite containing phosphine oxide moiety in the main chain was synthesized by a convenient ultraviolet irradiation technique.A precursor such as AgNO_3 was used as the source of the silver particles.Polyimide 6 as a source of polymer was synthesized by polycondensation reaction of bis（3-aminophenyl） phenyl phosphine oxide 4 with pyromellitic anhydride 5 in the presence of iso-quinoline as base and in m-cresol solution.The resulting composite film was characterized by FTIR spectroscopy,X-ray diffraction（XRD）,transmission electron microscopy（TEM）,thermogravimetry（TGA） and differential scanning calorimetry（DSC）.The average size of the nanometer Ag particles is about 10 nm.The temperature of 5 and 10%weight loss and also the char yield at 600℃of polyimide-silver nanocomposite 6a were higher than the pure PI 6.
基金This work is supported by the National Key Basic Program of China （No.2010CB922900） and the National Natural Science Foundation of China （No.91021008, No.i1274196, and No.iiiii120061）.
文摘A new 2-D variational method is proposed to calculate the vibrational energy levels of the symmetric P-H stretching vibration （vl） and the symmetric umbrella vibration （inversion vibration） （v2） of PH3^＋（^～X^2A″2） that has the tunneling effect. Because the symmetric internal Cartesian coordinates were employed in the calculations, the kinetic energy operator is very simple and the inversion vibrational mode is well characterized. In comparison with the often used I-D model to calculate the inversion vibrational energy levels, this 2-D method does not require an assmnption of reduced mass, and the interactions between the vl and v2 vibrational modes are taken into consideration. The calculated vibrational energy levels of PH3^＋ are the first reported 2-D calculation, and the average deviation to the experimental data is less than 3 cm^-1 for the first seven inversion vibrational energy levels. This method has also been applied to calculate the vibrational energy levels of NH3. The application to NH3 is less successful, which shows some limitations of the method compared with a full dimension computation.
