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.

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.

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.

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.

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.

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.

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.

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.

A novel thermoregulated phosphine ligand used for the Rh-catalyzed hydroformylation of mixed C_(11-12) olefins in aqueous/organic biphasic system

A novel thermoregulated phosphine ligand PhP(CHCHO)CH(n=22) was synthesized and used for the Rh-catalyzed hydroformylation of mixed Colefins in aqueous/organic biphasic system.Under the optimized conditions,pressure =5 MPa (H:CO=1:1),phosphine/Rh =13(molar ratio),reaction time =6 h and temperature =130℃,the conversion of Colefins and the yield of aldehyde are 99%and 94%,respectively.The catalyst retained in aqueous phase can be easily separated from the product-containing organic phase by simple phase separation and the catalytic activity remains almost constant after four consecutive cycles.

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.

Phosphine in various matrixes

Matrix-bound phosphine was determined in the Jiaozhou Bay coastal sediment, in prawn-pond bottom soil, in the eutrophic lake Wulongtan, in the sewage sludge and in paddy soil as well. Results showed that matrix-bound phosphine levels in freshwater and coastal sediment, as well as in sewage sludge, are significantly higher than that in paddy soil. The correlation between matrix bound phosphine concentrations and organic phosphorus contents in sediment samples is discussed.

A New Ternary Fluorescent Europium Complex with Bis(Diphenyl Phosphine Oxide) Methane and Thenoyltrifluoroacetone

A fluorescent ternary europium complex containing bis (diphenyl phosphine oxide) methane which functioned as both a neutral and anion ligand, and thenoyltrifluoroacetonato anion was synthesized and characterized by elemental analysis, DTA TG analysis, UV Vis, FT IR and MS spectroscopy. The chemical formula is proved to be Eu(TTA)(MPPO)(HMPPO)·(NO 3)·2H 2O. Its luminescence quantum efficiency(in acetonitrile, 26 3%) is approximately the same as that of the commonly used red emission luminescent compound, Eu(TTA) 3(TPPO) 2 (TPPO is triphenyl phosphine oxide). The new complex has comparatively long fluorescence lifetime.

Tri(t-butyl)phosphine-assisted selective hydrosilylation of terminal alkynes

A highly efficient and regio-/stereoselective method of hydrosilylating terminal alkynes was developed using Pt(DVDS)-tri(t-butyl) phosphine catalyst system at room temperature.Trans-products or alpha-products were obtained almost exclusively depending on the alkynes and silanes employed.

Chiral Phosphine Ligands Derived from Sugars 4.Crystal Structure of Methyl 4,6-O-Benzylidene-3-Deoxy-3-(Diphenylphosphino)-α-D-Altropyranoside (3-MBPA)

The crystal structure of the title compound 3--MBPA, C26H27O5P (Mr.= 450. 44 ). has been determined by single--crystal X-ray diffraction. The crystal ismonoclinic with space group P21, a= 9. 294(l), b= 7. 999(1), c= 15. 925(2) A,β=96. 17(5)°, V= 1176. 9 A 3, Dc=l. 271 g/cm3, F(000)=476, μ=12. 99 cm-1,Z=', Z=2, and final R = 0. 045 and Ru= 0. 057 for 1882 reflections (I≥3a(I) ). Structureanalysis revealed that the pyranose and 4, 6--O--benzylidene ring of the title compoundadopt a distorted chair conformation and the diphenylphosphino, OH and OMe groupsare in pseudo--axial position.

Chiral Phosphine Ligands Derived from Sugars8. Crystal and Molecular Structure of Diphenyl (methyl 4', 6'-O-benzylidene-2'-deoxy-α-D-altropyranoside-2-)phosphine Oxide

The crystal structure of the title compound, C26H27O6P, has been determined by single--crystal X-ray diffraction. The crystal is monoclinic with space groupP21, a=16. 193(l), b=5. 804(1), c=12. 512(2) A, β=93. 187(5)°, V=1174. 13A3, Dc=1. 319 g/cm3, F(000) =492, μ= 13. 52 cm-1, Z= 2, and final R= 0. 042and Rw= 0. 040 for 2349 reflections (I≥3σ(I)). Structure analysis revealed that thepyranose and 4, 6-O-benzylidene ring of the title compound adopts a distorted chair conformation.

Influence of low temperature on lethal time extension for different life stages of Cryptolestes ferrugineus (Stephens) with strong resistance to phosphine fumigation

Knowing the time extension degree of full mortality in phosphine fumigation at low temperature significantly contributes to successful insect pest control,especially for reducing fumigation failure and inhibiting resistance development.The comparison ofmortality and lethal time on eggs,larvae,pupae and adults of Cryptolestes ferrugineus(Stephens)was conducted,and the strain with 1043 times of resistance factor to phosphine was assayed during fumigation with 300 mL/m^3 of phosphine concentration at 18,23 and 28℃.The LT50 values to eggs,larvae,pupae and adults of C.ferrugineus at 18℃ were postponed by 2,2,1 and 5 d comparedwith that at 23℃,and 5,4,5 and 7 d compared with that at 28℃,respectively.The LT99 values to eggs,larvae,pupae and adults at 18℃ were 5,1,2 and 7 d longer than that at 23℃,and 6,5,5 and 10 d longer than that at 28℃,respectively.The lethal time of different life stages of the C.ferrugineus strain significantly increased with temperature decreasing.The exposure time of full mortality on pupae at 300 mL/m^3 of phosphine at 18℃ reached 38 d,which was 12 d longer than that of larvae.The order of tolerance of different life stages of C.ferrugineus exposed to 300 mL/m^3 phosphine from high to low was pupae,eggs,adults,larvae at tested temperatures.

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.

Three-Component Coupling Catalyzed by Phosphine: Preparation of α-Amino γ-Oxo Acid Derivatives

The three-component coupling reaction of ethyl propiolate (1), phthalimide (2), and aldehyde (3) catalyzed by tripheny- lphosphine, was developed. A solution of an equivalent amount of 1 and 2 in benzaldehyde (3a) in the presence of 30 mol% of PPh3 was heated at 100?C for 48 h to give N-(1-ethoxycarbonyl-3-oxo-3-phenylpropyl)phthalimide (4a) in 83% yield. This reaction was thought to proceed via vinylphosphonium salt formed from the reaction of ethyl propiolate (1) with triphenylphosphine in situ.

Research on the Inert Dust against Phosphine Resistance of Cryptolestes Ferrugineus

Laboratory tests were carried out in order to evaluate the efficacy of five inert dust （Puliangtai, G-1, G-2, G-3 and G-4） against the high level phosphine resistance Cryptolestesferrugineus （Stephens）. The relative phosphine resistance of two strains of Cryptolestesferrugineus （Stephens） was measured by the method of knockdown at 2 mg/L of phosphine. The insects were exposed to the five inert dust on filter paper inside petri dishes for 1 day at 30 ±1℃and 65 ±1% relative humidity. Then, the adults were held for 4 days with food at the same conditions without inert dust in surface bioassay. Also, they were placed in 25 ±1℃ and 65 ±1% relative humidity in grain bioassay. In surface bioassay, two strains （JXCF and YYCF） ofCryptolestesferrugineus （Stephens） were susceptible to the five inert dust at 0.08 g/m2 and 0.1 g/m2. G-3 appeared the most effective treatment against both strains, since its efficacy was 3-6 times higher than the other four inert dust tested. YYCF strain was more susceptible than JXCF, with 1-4 times higher mortality level. This research indicated that inert dusts were effective on phosphine-resistance Cryptolestesferrugineus （Stephens） populations.