Alkoxy substituted MeO-BIPHEP-type diphosphines ligands for asymmetric hydrogenation of aryl ketones

In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.

Groups-dependent phosphines as the organic redox for point defects elimination in hybrid perovskite solar cells

Lead(Pb)^(0) and iodine(I)^(0) point defects generated during perovskite solar cell(PSC)fabrication and photoconversion form deep band energy levels as the carriers’recombination centers.These defects not only deteriorate device efficiency,but also facilitate chemical degradation with ion migration,resulting in restricted device lifetime.Herein,we present a novel type of phosphines as the point defects stabilizer for hybrid perovskite solar cells with enhanced performances.Three phosphines with varied side groups of tributyl,trioctyl and triphenyl are exampled as the dopants in perovskite films.The group dependent redox properties were observed in the perovskite film,dependent on their molecular weights and steric hinderances of phosphines.The partially oxidized tributyl phosphine(TBUP)with additional tributyl phosphine oxides(TBPO)is efficient in reduction of lead(Pb)^(0) and iodine(I)^(0) concentrations during the device fabrication and operation.The device with TBUP-TBPO pair showed enhanced power conversion efficiency(PCE)to 20.48% and maintain 91.7% of their initial PCEs after 500 h at 65℃ thermal annealing.Thus,this work presents an efficient route of utilize the phosphine species to reduce point defects in the perovskite film,which promoting further development of novel phosphorous additives with defects stabilization,interface passivation and encapsulation for low-cost solution processed PSCs.

Some New Water-Soluble Phosphines with the Involvement of the Trivalent Rare Earth Ion

The new type of water-soluble phosphine with the involvement of the trivalent rare earth ion, TPPTS?Ln (Ln=Eu, Dy, Er, Tm, Yb, Lu; and TPPTS=tris (m-sulfonatophenyl) phosphine), were synthesized from the precursor TPPTS?Na3 and oxides of rare earth. The chemical composition of TPPTS?Ln was determined by elemental analysis and ICP-AES. IR, Raman showed that the sulfonate group in the complexes was a tridentate ligand.31P NMR, TG-DTA, molar conductivity and the fluorescence of these complexes were also recorded and discussed.

Divergent intramolecular reactions between phosphines and alkynes

A divergent intramolecular reaction of phosphine tethered alkyne in protic solvent was developed.This provided a novel and simple access to a large variety of(Z)-alkenylphosphine oxides and phospholane oxides.Our preliminary studies suggested that these divergent reactions are closely related to the reaction condition and molecular structure.A possible mechanism of C-P bond cleavage of a pentacoordinated hydroxyphosphorane intermediate was proposed.

Syntheses of a new type of chiral phosphines from glucose

Methyl 3-deoxy-3-(diphenylphosphino)-4,6-O-benzylidene-alpha-D-altropyranoside (1) and methyl 2-deoxy-2-(diphenylphosphino)-4,6-O-benzylidene-alpha-D-altropyranoside (2) were prepared from methyl 2,3-anhydro-4,6-O-benzylidene-O-D-mannopyranoside and methyl 2,3-anhydro-4,6-O-benzylidene-alpha-D-allopyranoside, respectively, via regioselective and stereospecific ring-opening reactions in high yields. Compounds 1 and 2 were oxidized to give the corresponding phosphine oxides (3 and 4).

High-performance liquid-phase catalytic purification of phosphine in tail gas using Pd(Ⅱ)/Cu(Ⅱ)composite

Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully explored and pioneered.The catalytic performance,thermodynamics,kinetics,and catalytic oxidation mechanism of Pd/Cu liquid-phase catalyst catalytic oxidation of PH_(3) were thoroughly investigated.The results showed that Pd/Cu has a superior catalytic effect on the removal of PH_(3) in the gas mixture under low temperature.With CO as the carrier gas,the removal efficiency of PH_(3) could be maintained at 100%for nearly 450 min,indicating that the Pd/Cu liquid phase catalyst has good resistance to heterotoxicity.According to the thermodynamic,kinetic,and related characterization results of the PH_(3) purification process,the kinetic region of the gas–liquid reaction of PH_(3) absorption by Pd/Cu solution was an interfacial reaction.Pd was the primary catalyst and Cu was the secondary catalyst,and the adsorption of PH_(3)was a primary reaction.PH_(3) was spontaneously oxidized to H_(3)PO_(4) in the Pd/Cu catalytic system during the removal process.Pd was regenerated by O_(2) and Cu,increasing the activity and stability of the Pd/Cu catalyst in the sustain and efficient purification of PH_(3) in tail gas.

Effect of lengthening alkyl spacer on hydroformylation performance of tethered-phosphine modified Rh/SiO_2 catalyst

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.

Efficient and recyclable Rh-catalytic system with involvement of phosphine-functionalized phosphonium-based ionic liquids for tandem hydroformylation—acetalization

The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.

Ionic palladium complex as an efficient and recyclable catalyst for the carbonylative Sonogashira reaction

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.

Killing Effect of Mixed Fumigation of Phosphine and Carbon Dioxide on Eggs of Lasioderma serricorne F.

[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.

Effects of Phosphine on Germination and Physiological Characteristics of Rice Seeds

[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.

Characterization of Metal Oxide-modified Walnut-shell Activated Carbon and Its Application for Phosphine Adsorption: Equilibrium, Regeneration, and Mechanism Studies

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.

Preparation of nanometer FeCuP alloy and its application in decomposition of PH3

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%.

Stimulation of gaseous phosphine production from Antarctic seabird guanos and ornithogenic soils

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.

Polyimide-silver nanocomposite containing phosphine oxide moieties in the main chain:Synthesis and properties

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.

Inversion Vibrational Energy Levels of PH3^＋（^～X^2A″2） Calculated by a New Two-dimension Variational Method

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.

Henry's Law constant for phosphine in seawater:determination and assessment of influencing factors

The Henry＇s Law constant （k） for phosphine in seawater was determined by multiple phase equilibration combined with headspace gas chromatography. The effects of pH, temperature, and salinity on k were studied. The k value for phosphine in natural seawater was 6.415 at room temperature （approximately 23℃）. This value increases with increases in temperature and salinity, but no obvious change was observed at different pH levels. At the same temperature, there was no significant difference between the k for phosphine in natural seawater and that in artificial seawater. This implies that temperature and salinity are major determining factors for k in marine environment. Double linear regression with Henry＇s Law constants for phosphine as a function of temperature and salinity confirmed our observations. These results provide a basis for the measurement of trace phosphine concentrations in seawater, and will be helpful for future research on the status of phosphine in the oceanic biogeochemical cycle of phosphorus.

Study on Critical Properties for CO_2+Cosolvent Binary System and Ternary System

The performance of supercritical fluid (SCF) as a solvent can be greatly affected by addition of anentrainer to the system. In this study, a constant volume visual method is used to measure the critical point ofCO2+n-butyraldehyde, CO2+ i-butyraldehyde and CO2+alcohol binary systems and CO2+entrainer+trisodiumsalt of tri-(m-sulfonphenyl)phosphine (TPPTS) ternary systems, which provides us good theoretical basis for super-critical extraction and chemical reaction. The relationship between critical point and concentration of the entrainerare discussed. The phase behavior of binary system and that of ternary system are compared. The relationshipbetween the concentration of TPPTS and critical point of binary systems are also discussed.

Extraction and Separation of Thorium and Ytterbium with Bis(2,4,4-Trimethylpentyl) Phosphinic Acid Using a Hollow Fiber Membrane Extractor

The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The separation operation of Th 4+ and Yb 3+ mixture was carried out by two successive extraction and stripping simultaneously. The concentration ratio of Th 4+ to Yb 3+ is 16 74 in the stripping solution. The recovery and purity of Th 4+ are 71 6% and 95 74% respectively.

Study of Transport and Separation of Rare Earth Ions through the Emulsion Liquid Membrane of Bis(2,4,4-trimethylpentyl)phosphinic Acid-Span 80-Toluene

It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapidly was realized under the optimum experimental conditions:1.0×10^(-3)～3.0×10^(-3)mol/L bis(2,4,4-trimethylpentyl)phosphinic acid and 2%～4%(W/V)Span 80 in toluene solution as membrane phase,0.50～2.0 mol/L HCl as inner phase,rare earth ion solutions with pH 3.5～5.0 as outer phase.Ac- cording to the differences of transport behavior for rare earth ions,it is possible to separate rare earth ions from mixed solutions of rare earth ions by this liquid membrane system.