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.

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.

Cu-catalyzed arylation of phosphinic amide facilitated by (±)-trans-cyclohexane-1,2-diamine

Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10 times in Cu-catalyzed cross coupling.

Synthesis and Crystal Structure of α-(3-Phenylureido)-α-(2,4-Dichlorophenyl) Methyl Phenylphosphinic Acid

The crystal structure of a (3-phenylureido)-a (2, 4-dichlorophenyl)methyl phenylphosphinic acid, C20H17Cl2N2O3P, Mr= 435. 25,which was obtained bydesulphurisation of cis-3, 4-dipheny1-5- (2, 4-dichlorophenyl ) -1, 3, 4-diazaphospholidin2-thione-4-oxide utilizing Ag+ -H2O system in a yield of 89%, is reported. It crystallizes in orthorhombic space group Pca21 with a= 11. 286(2), b= 20. 601 (4) f c=8. 695(2)A, V= 2021 (1) A3, Z= 4, D.= 1. 430 g/cm3, p=4. 21 cm-1, F(000) =896.The final R factor is 0. 040 and Rw is 0. 045 for 946 unique observed reflections[I>3a(I)]. The result of X-ray analysis indicates that the molecules in the crystal are linkedtogether by the O(3 ) ...H (2d) - N (2d ) intermolecular hydrogen-bondings.

Separation of Tb^(3+) , Dy^(3+) , Ho^(3+) , Er^( 3+) with Solvent Impregnated Resins Containing Di-(2,4,4-trimethylpentyl) Phosphinic Acid

Solvent impregnated resins (SIR) with di (2,4,4 trimethylpentyl)phosphinic acid (Cyanex 571) were studied by adsorption of the extractant into Amberlite XAD 4; XAD 7; XAD 1180 polymeric adsorbents. The results shas that Cyanex 571/XAD 7 impregnated resins containing extractant of 0 35～0 45 g·g -1 resin have a favorable extractive activity in HCl medium. The rare earths (Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ ) are separated by using SIR as the column stationary phase. The better separation effect is obtained at lower load and slower elution rate.

SYNTHESES OF HINDERED ALKYL PHOSPHONATES AND PHOSPHONIC & PHOSPHINIC ACIDS

A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.

Extractant(2,3-dimethylbutyl)(2,4,40-trimethylpentyl) phosphinic acid(INET-3) impregnated onto XAD-16 and its extraction and separation performance for heavy rare earths from chloride media

（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight（LMW） polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography（GPC）. The macroporous resins（XAD-16 ＆ Pre-XAD-16）, the corresponding solvent impregnated resins（SIRs-INET-3/XAD-16 ＆SIRs-INET-3/Pre-XAD-16） and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE（III） adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm（III） adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm（III） adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE（III） on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm（III） accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE（III） β（Er/Ho）, β（Tm/Er）, β（Yb/Tm） and β（Lu/Yb） values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu（III） onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H2SO4.

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.

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.

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.

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.

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.

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.

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 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.

Studies on the Recycling Efficiency of Thermoregulated Phase-separable Rh/PETPP Complex Catalyst

Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP (P-[p-C6H4O(CH2CH2O)nH]3, N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented. It was found that the loss of Rh is dependent greatly on the composition of phosphine ligand PETPP and the organic solvent employed in the reaction.

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.

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.