Studies on Adsorption Behavior and Mechanism of Copper(Ⅱ) onto Amino Methylene Phosphonic Acid Resin

The adsorption behavior and the mechanism of a novel chelate resin, amino methylene phosphonic acid resin(APAR) for Cu(Ⅱ) were investigated. Cu(Ⅱ) was quantitatively adsorbed by APAR in the medium of pH=4 09. The statically saturated adsorption capacity is 181 mg/(g resin). Cu(Ⅱ) adsorbed on APAR can be eluted by 1 0-3 0 mol/L HCl. The rate constant is k 298 =5 58×10 -5 s -1 . The adsorption of Cu(Ⅱ) on APAR follows the Freundlich isotherm. The Δ H of the adsorption is 3 91 kJ/mol. The apparent activation energy is E a=21 4 kJ/mol. The coordination molar ratio of APAR to Cu(Ⅱ) is 1/1. It is shown that the nitrogen and the oxygen atoms in the functional group of APAR coordinate to Cu(Ⅱ).

CORROSION BEHAVIOR OF A ZIRCONIUM-TITANIUM BASED PHOSPHONIC ACID CONVERSION COATING ON AA6061 ALUMINIUM ALLOY

The conversion coating was formed by dipping AA6061 in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid （ATMP） solution at room temperature. The formation process and the anti-corrosion performance of the conversion coating were investigated using electrochemical test and salt spray test （SST）, respectively. The electrochemical test shows that the Zr/Ti and ATMP coating improves the corrosion resistance of AA6061 as good as the chromate （VI） coating. But the results of SST show that the corrosion resistance of Zr/Ti and ATMP coating is not as good as the chromate （VI） coating. The corrosion area is less than 2% after 72 h.

Sorption Behavior and Mechanism of Indium(Ⅲ) onto Amino Methylene Phosphonic Acid Resin

The sorption behavior of amino methylene phosphonic acid resin (APAR) for In (Ⅲ ) was investigated . Experimental results show that In ( Ⅲ ) adsorbed on APAR can be elated with 2mol · L -1 HCl. The apparent rate constant is k29 = 1.50 × 10-5s-1. The sorption behavior of APAR for In ( Ⅲ ) obeys the Freundlich isotherm. The themodynamic parameters of sorption, enthalpy change ()H, free energy change ()G and entropy change ()S of sorption (APAR) for In ( Ⅲ ) are 24.1 kJ·mol-1, -35. 1kJ· mol-1 and 200J· mol-1·K-1 respectively. The coordination molar ratio of the functional group of APAR to In( Ⅲ ) is 2:1. The sorption mechanism of APAR for In( Ⅲ ) was examined by IR spectrometry.

Adsorption of Macroporous Phosphonic Acid Resin for Nickel

Tje adsorption bchavior and mechanism of a novel chelate resin,macroporous phosphonic acid resin（PAR）for Ni（Ⅱ）were imestigated.The stotically saturated adsorption capacity is 64.3mg·g^-1 resin at 298K in HAc-NaAc medium.The Ni（Ⅱ）adsorbed on PAR can be eluted by 0.5mal·L^-1 HCl and the elution percentage reaches 96.6%.The resin can be regenerated and reused without abvious decrease in adsorption capacity.The apparent adsorption rate constant is k298=2.6×10^-5s^-1.The adsorption behavior of PAR for Ni（Ⅱ）obeys the Freundllich isotherm.The thermodynamie adsorption parameters.enthalpy change △H,free energy change △G and entropy change △S of PAR for Ni（Ⅱ）are 3.36kJ·mol^-1,-5.47kJ·mol^-1 and 29.6J·mol^-1·K^-1,respectively.The apparent activation energy is Ea=12.2kJ·mol^-1,The molar coordination ratio of the functional group of PAR to Ni（Ⅱ）is about 4：1.The adsorption mechanism of PAR for Ni（Ⅱ）was examined by a chemical method and IR spectrometry.

Studies on the Adsorption of Amino Methylene Phosphonic Acid Resin for Holmium(Ⅲ)

The adsorption behavior and mechanism of a novel chelate resin, amino methylene phosphonic acid resin (APAR) for Ho(Ⅲ) were investigated. The statically saturated adsorption capacity is 258 mg·g^(-1) resin at 298 K in HAc-NaAc medium. The Ho(Ⅲ) adsorbed on APAR can be repeatedly eluted by 3.0 mol·L^(-1) HCl and the elution percentage is as high as 95.8%. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=1.14×10^(-5) s^(-1). The adsorption behavior of APAR for Ho(Ⅲ) obeys the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change ΔH of APAR for Ho(Ⅲ) is 11.4 kJ·mol^(-1). The apparent activation energy is E_a=15.8 kJ·mol^(-1). The molar coordination ratio of the functional group of APAR to Ho(Ⅲ) is about 2∶1. The adsorption mechanism of APAR for Ho(Ⅲ) was examined by using chemical method and IR spectrometry.

Synergistic extraction of praseodymium with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline

The synergistic extraction of Pr^3＋ from hydrochloric medium using mixture of 2-ethylhexyl phosphonic acid mono- 2-ethylhexyl ester （P507, HL） and 8-Hydroxyquinoline （HQ） in heptane was investigated. The effect of equilibrium of aqueous acidity on extraction of Pr^3＋ was discussed. The effect of extractant concentraction, different diluents, equilibrium time and acetate ion concentration oil extraction reaction were also studied. With a method of double-logarithmic slope, composition of the extracted species on 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline was derived. The result shows that the synergistic extraction system not only overcomes emulsification of 8-Hydroxyquinoline, but also shows perfect capacity of synergistic extraction. The largest synergistic enhancement factor can be calculated to be 5.49 at pH 3.6 for Pr^3＋.

Novel Phosphonoacetic Acid Derivatives.Synthesis of N-(Ethoxycarbonylmethylphosphonyl)-α-Amino Esters and-α-Amino Phosphonic Acid Esters and Their Bioactivities

A series of novel phosphonoacetic acid derivatives, N-(ethoxycarbonylmethy-ethoxyphosphonyl)-α-amino acid esters and α-amino phosphonates, were synthesized via the reaction of the corresponding phosphonyl chloride with amino acid ester hydrochlorides or amino phosphonates in the presence of a base. The preliminary bioassay shows that some compounds show significant anti-viral activity against tobacco mosaic virus (TMV)

Efficient and stable organic solar cells enabled by a poly(carbazole phosphonic acid)hole transporter

Conventional self-assembled monolayer(SAM)hole transporters in organic solar cells(OSCs)generally suffer from poor uniformity and limited thickness tolerance,hindering their large-scale production.To overcome these limitations,we introduce a novel polymeric hole transporter synthesized by polymerizing carbazole phosphonic acid(PACz).The resultant Poly-2PACz material exhibits exceptional conductivity,high tolerance for variations in layer thickness,and improved film uniformity compared with conventional SAMs.Consequently,the OSCs utilizing Poly-2PACz achieve a remarkable power conversion efficiency of 19.1%and a high fill factor of 81.2%,surpassing the devices based on 2PACz.Moreover,Poly-2PACz-based OSCs demonstrate excellent operational stability,retaining over 80%of their initial efficiency after 1,400 h of continuous light exposure in ambient conditions.This work presents a novel strategy for designing hole transporters,paving the way for more efficient and stable OSCs.

Adsorption Behaviors and Mechanism of Macroporous PhosphonicAcid Resin for Gadolinium

The adsorption behaviors and mechanism of a novel chelate resin, macroporous phosphonic acid resin(PAR)for Gd(Ⅲ)were investigated. The statically and dynamically saturated adsorption capacity is respectively 308 mg·g^(-1)resin and 296 mg·g^(-1)resin at 298 K in HAc-NaAc medium at pH 5.6. Gd(Ⅲ)adsorbed on PAR can be reductively eluted by 0.5～5.0 mol·L^(-1) HCl used as eluant and the elution percentage is up to 94.7% in 1.0 mol·L^(-1) HCl. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=3.96×10^(-5) s^(-1). The adsorption behavior of PAR for Gd(Ⅲ) conforms to the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change △H of PAR for Gd(Ⅲ)is 22.6kJ·mol^(-1). The apparent adsorption activation energy(Ea)of PAR for Gd(Ⅲ)is 5.0 kJ·mol^(-1). The molar coordination ratio of the functional group of PAR to Gd(Ⅲ)is about 3∶1. The adsorption mechanism of PAR for Gd(Ⅲ)was examined by using chemical method and IR spectrometry.

Extraction Separation of Scandium，Iron and Lutetium with Isopropyl Phosphonic Acid Mono（1－hexyl－4－ethyl）OctylEster

The extraction and stripping of scandium from its sulfate solutions by isopropyl phosphonic acid mono (1-hexyl-4-ethyl) octyl ester (PT-2, HL) diluted with n-hexane are reported. A high efficiency of separation between scandium, iron and lutetium can be achieved by controlling aqueous acidity. Different mechanisms of Sc3+ with PT-2 in various acid range have been proposed.At lower aqueous acidity, it is a cation exchange reaction, while at higher acidity. a solvation reaction was ascertained. Its IR and NMR spectra have been discussed. The effect of temperature on extraction of Sc3+ was observed and thermodynamic functions were calculated.

PREPARATION AND CHARACTERIZATION OF HUMIDITY SENSOR BASED ON POLY(3-ALKYL)PYRROLE CONTAINING PHOSPHONIC ACID GROUPS

Poly（3-alkyl）pyrroles containing phosphonic acid groups with different alkyl segment lengths were chemical synthesized and the properties were measured by FTIR and UV-Vis spectroscopy. FTIR and UV-Vis results showed that the synthesized polymers were in a low doping level through chemical polymerization. By spin-coating on the surface of substrates, the polymer can be used as a humidity sensor. The change of DC electric current of the polypyrroles varies with the chain length of the alkyl substituents. The capacitance increases with the increase of the humidity and resistance decreases with the increase of humidity. This result is different from that ofpolypyrrole without alkyl substituents due to the influence of the phosphonic acid group. The sensor showed the resistive-type at high relative humidity, and the capacitive- type at the low relative humidity. The sensor exhibited very fast response to the change of environment humidity.

ADO-phosphonic acid self-assembled monolayer modified dielectrics for organic thin film transistors

This study explores a strategy of using the phosphonic acid derivative （11-（（12-（anthracen-2- yl）dodecyl）oxy）-11-oxoundecyl） phosphonic acid （ADO-phosphonic acid） as self-assembled monolayers （SAMs） on a Si/SiO2 surface to induce the crystallization ofrubrene in vacuum deposited thin film transistors, which showed a field-effect mobility as high as 0.18 cm2/（V.s）. It is found that ADO-phosphonic acid SAMs play a unique role in modulating the morphology ofrubrene to form a crystalline film in the thin-film transistors.

Synthesis of a Novel Perfluorinated Vinyl Ether Containing Sulfonimide and Phosphonic Acid Functionalities

The novel perfluorinated vinyl ether containing sulfonimide and phosphonic acid functionalities, CF2 = CFOCF2CF(CF3)-OCF2CF2SO2NHSO2(CF2)2P(O)(OH)2, has been synthesized by multiple reaction steps. It is a very strong bi-functional acid and exhibits a high degree of stability in aqueous solution at an elevated temperature. These properties make it an attractive monomer for the preparation of the co-polymer with TFE to obtain the high quality ionomer membrane and proton conductor.

Separation of La(Ⅲ),Ce(Ⅳ)and Ca(Ⅱ)from bastnaesite using acidic phosphonic chitosan and rotating disk membrane

The separation of rare earths is difficult due to their similar properties and the complex characteristics of associated vein o res.Complexation-ultrafiltration(CUF)and shear induced o rderly dissociation coupling with ultrafiltration(SIODUF)were used to separate metal ions(M,M=La(Ⅲ),Ce(Ⅳ)and Ca(Ⅱ))from simulated bastnaesite leaching solution using acidic phosphonic chitosan(aPCS)and rotating disk membrane.Effect of simultaneous removal of metallic ions was investigated by CUF,and suitable conditions were obtained for C/M 10.0(mass ratio of complexant to metal ions)and pH 5.0.The shear stabilities of aPCS-M complexes were explored at different pH values and the results show that the complexes can dissociate at a certain rotational speed,the critical one.The critical s hear rates of aPCS-La,aPCS-Ce and aPCS-Ca complexes at pH 5.0 were calculated as 1.42×10^(5).1.69×10^(5) and 9.75×10^(4) s~(-1),respectively.The order of complexes shear stability is aPCS-Ca aPCS-La<aPCS-Ce.The high selective separation of M and regeneration of aPCS were achieved by SIODUF in the light of the difference of aPCSM complexes shear stabilities.The separation coefficientsβa/ce andβca/La reach 31.2 and 53.9,respectively.

Structural investigation of the zirconium-titanium based amino trimethylene phosphonate hybrid coating on aluminum alloy

A zirconium-titanium based amino trimethylene phosphonate hybrid coating on AA6061 aluminum alloys was formed by dipping in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid （ATMP） solution for improving the lacquer adhesion and corrosion resistance as a substitute of chromate coatings. The morphology and structure of the hybrid coating were studied by means of scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The surface composition and structure characteristics were also investigated by means of X-ray photoelectron spectroscopy （XPS） and Fourier transformation infra-red spectroscopy （FTIR）. The results of SEM and AFM show that the hybrid coating present piece particle distribution which is much denser than that of the zirconium-titanium coating. The results of XPS and FTIR indicate that the hybrid coating is a hybrid composite structure composed of both the zirconium-titanium and amino trimethylene phosphonate coatings.

Efficient wide-bandgap perovskite solar cells with open-circuit voltage deficit below 0.4 V via hole-selective interface engineering

Wide-bandgap mixed-halide perovskite solar cells(WBG-PSCs)are promising top cells for efficient tandem photovoltaics to achieve high power conversion efficiency(PCE)at low cost.However,the open-circuit voltage(V_(OC))of WBG-PSCs is still unsatisfactory as the V_(OC)-deficit is generally larger than 0.45 V.Herein,we report a buried interface engineering strategy that substantially improves the V_(OC)of WBG-PSCs by inserting amphiphilic molecular hole-selective materials featuring with a cyanovinyl phosphonic acid(CPA)anchoring group between the perovskite and substrate.The assembly and redistribution of CPA-based amphiphilic molecules at the perovskite-substrate buried interface not only promotes the growth of a low-defect crystalline perovskite thin film,but also suppresses the photo-induced halide phase separation.The energy level alignment between wide-bandgap perovskite and the hole-selective layer is further improved by modulating the substituents on the triphenylamine donor moiety(methoxyls for MPA-CPA,methyls for Me PA-CPA,and bare TPA-CPA).Using a 1.68 e V bandgap perovskite,the Me PA-CPA-based devices achieved an unprecedentedly high V_(OC)of 1.29 V and PCE of 22.3%under standard AM 1.5 sunlight.The V_(OC)-deficit(<0.40 V)is the lowest value reported for WBG-PSCs.This work not only provides an effective approach to decreasing the V_(OC)-deficit of WBG-PSCs,but also confirms the importance of energy level alignment at the charge-selective layers in PSCs.

A metal-OH group modification strategy to prepare highly-hydrophobic MIL-53-Al for efficient acetone capture under humid conditions

A series of highly-hydrophobic MIL-53-Al(MIL = Materials of Institut Lavoisier) frameworks synthesized via decoration of the Al-OH groups by alkyl phosphonic acid were developed as adsorbents for removing acetone from humid gas streams.The newly prepared materials were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), scanning electron microscope(SEM), N_(2) adsorption-desorption and thermogravimetric analysis(TGA).Their adsorption behaviors toward acetone vapor under dry and wet conditions were studied subsequently.Results showed that alkyl phosphonic acid was successfully grafted into MIL-53-Al skeleton through coordinating interaction with Al3+generating MIL-53-Al@C_(x)(x = 12, 14, 18).The MIL-53-Al@C_(x) exhibited similar crystal structure and thermal stability to parent MIL-53-Al.Furthermore, the modified materials showed significantly enhanced hydrophobicity.The water vapor uptake of MIL-53-Al@C_(14) decreased by 72.55%at 75% relative humidity(RH).Dynamic adsorption experiments demonstrated that water vapor had almost no effect on the acetone adsorption performance of MIL-53-Al@C_(14).Under the condition of 90% RH, the acetone adsorption capacity of MIL-53-Al@C_(14) was 102.98% higher than that of MIL-53-Al.Notably, MIL-53-Al@C_(14) presented excellent adsorption reversibility and regeneration performance in 10 adsorption-desorption cycles.Taken together, the strategy of metal-OH group modification is an attractive way to improve the acetone adsorption performance over metal-organic frameworks(MOFs) under humid conditions.Besides, MIL-53-Al@C_(14) would be deemed as a promising candidate for capturing acetone in high moisture environment.

Novel and Convenient Approach to Synthesis of AZT/d4T H-phosphonates

A convenient, efficient and general method has been developed for synthesis of H-phosphonate mono and diesters of AZT and d4T through one-pot reaction of phosphonic acid with AZT or d4T and different alcohols using pivaloyl chloride as condensing agent under mild conditions.

Separation and recovery of rare earth from waste nickel-metal hydride batteries by phosphate based extraction-precipitation

A novel type of extraction-precipitation strategy based on phosphate was developed to recover rare earth(RE,i.e.,La,Ce,Nd,and Pr)from waste nickel-metal hydride(NiMH)batteries.This method does not require saponification and organic solvents.The novel phosphates,i.e.,dibenzyl phosphate(DBP),diphenyl phosphate(DPP),triphenyl phosphate(TPP)were studied as extraction-precipitants.DBP has high precipitation efficiencies for RE^(3+),which can reach 97.84%,100%,100%and 99.77%,respectively.In addition,the precipitation efficiencies of Mn^(2+),Co^(2+)and Ni^(2+)are less than 1.75%.DBP-RE has the largest particle size(D10=52.6μm,D50=135.35μm,D90=296.08μm),which is much larger than the precipitations formed by NH_(4)HCO_(3),H_(2)C2O_(4),CaO and MgO.The larger precipitation particle sizes contribute to improving the solid-liquid separation efficiency.With 3 mol/L hydrochloric acid,the stripping efficiency of DBP-RE reaches 98.60%,and the purity of recovered RE is 99.85%.The regenerated DBP can be directly used for the recycling extraction.Therefore,the novel extraction-precipitation strategy is a green and sustainable separation method.