Intermolecular Acid-Base-Pairs Containing Poly(p-Terphenyl-co-lsatin Piperidinium)for High Temperature Proton Exchange Membrane Fuel Cells

How to optimize and regulate the distribution of phosphoric acid in matrix,and pursuing the improved electrochemical performance and service lifetime of high temperature proton exchange membrane(HT-PEMs)fuel cell are significant challenges.Herein,bifunctional poly(p-terphenyl-co-isatin piperidinium)copolymer with tethered phosphonic acid(t-PA)and intrinsic tertiary amine base groups are firstly prepared and investigated as HT-PEMs.The distinctive architecture of the copolymer provides a well-designed platform for rapid proton transport.Protons not only transports through the hydrogen bond network formed by the adsorbed free phosphoric acid(f-PA)anchored by the tertiary amine base groups,but also rely upon the proton channel constructed by the ionic cluster formed by the t-PA aggregation.Thorough the design of the structure,the bifunctional copolymers with lower PA uptake level(<100%)display prominent proton conductivities and peak power densities(99 mS cm^(-1),812 mW cm^(-2)at 160℃),along with lower PA leaching and higher voltage stability,which is a top leading result in disclosed literature.The results demonstrate that the design of intermolecular acid-base-pairs can improve the proton conductivity without sacrificing the intrinsic chemical stability or mechanical property of the thin membrane,realizing win-win demands between the mechanical robustness and electrochemical properties of HT-PEMs.

Activating Ru in the pyramidal sites of Ru_(2)P-type structures with earth-abundant transition metals for achieving extremely high HER activity while minimizing noble metal content

Rational design of efficient pH-universal hydrogen evolution reaction catalysts to enable large-scale hydrogen production via electrochemical water splitting is of great significance,yet a challenging task.Herein,Ru atoms in the Ru_(2)P structure were replaced with M=Co,Ni,or Mo to produce M_(2-x)Ru_(x)P nanocrystals.The metals show strong site preference,with Co and Ni occupying the tetrahedral sites and Ru the square pyramidal sites of the CoRuP and NiRuP Ru_(2)P-type structures.The presence of Co or Ni in the tetrahedral sites leads to charge redistribution for Ru and,according to density functional theory calculations,a significant increase in the Ru d-band centers.As a result,the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru_(2)P in both acidic and alkaline media.The effect is not observed for MoRuP,in which Mo prefers to occupy the pyramidal sites.In particular,CoRuP shows state-of-the-art activity,outperforming Ru_(2)P with Pt-like activity in 0.5 M H_(2)SO_(4)(η10=12.3 mV;η100=52 mV;turnover frequency(TOF)=4.7 s^(-1)).It remains extraordinarily active in alkaline conditions(η10=12.9 mV;η100=43.5 mV)with a TOF of 4.5 s^(-1),which is 4x higher than that of Ru_(2)P and 10x that of Pt/C.Further increase in the Co content does not lead to drastic loss of activity,especially in alkaline medium,where,for example,the TOF of Co_(1.9)Ru_(0.1)P remains comparable to that of Ru_(2)P and higher than that of Pt/C,highlighting the viability of the adopted approach to prepare cost-efficient catalysts.

Doping PCBM with fullerene phosphinate derivatives enhances the interface energy alignment and synergistic passivation capability

Phenyl-C_(61)-butyric acid methyl ester(PCBM) serves as a common electron transport layer(ETL) in inverted p-i-n structure perovskite solar cells(IPSCs),yet energy barriers and insufficient passivation at the PCBM-perovskite interface hinder device effectiveness and durability.In this study,we present a series of novel Fullerene Phenylacid Ester Derivatives(FPEDs:FPP,FTPP,FDPP) incorporated into PCBM.Our investigations illustrate that FPEDs effectively act to passivate the perovskite surface by forming robust interactions with uncoordinated Pb^(2+) ions via the phosphine oxide groups present in their molecular structures,thereby enhancing the stability of the devices.Moreover,these additives elevate the energy level of the lowest unoccupied molecular orbital(LUMO) of ETL,diminish the electron injection barrier,and enhance the efficiency of interlayer electron transport.Incorporating FPEDs enhances ETL coverage on the perovskite layer,reducing leakage current significantly.Notably,Devices with PCBM/FTPP achieved a peak PCE of 23.62% and showed superior stability,maintaining 96,8% of the initial PCE after 500 h,while control devices retained merely 80.7% over the same period.

Aminated Cyclopropylmethylphosphonates as Potent Prostate Cancer Inhibitors

Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).

Photoinduced transition-metal and external photosensitizer free phosphonation of unactivated C(sp^(2))-F bond via SET process under mild conditions

Transition-metal catalyzed cross-couplings of aryl halides(ArI,ArBr and ArCl)with a broad range of nucleophiles have been developed as powerful methods for carbon-carbon and carbon-heteroatom bonds formation.However,due to the high bond dissociation energy of unactivated C(sp^(2))-F,cross-couplings of mono-fluoroarenes are the most challenging,especially without using transition-metal catalysts.Herein,a photo-induced transition-metal and external photosensitizer free defluorophosphonation of monofluoroarenes via unactivated C(sp^(2))-F bond cleavage is reported.Different mono-fluoroarenes have been successfully cross-coupled with dialkyl phosphites in moderate to excellent yields under mild conditions.Mechanistic studies have revealed the possible involvement of a photo-induced SET process and aryl free radical intermediates.

Self-Assembling Molecules Boost Perovskite Solar Cell Efficiency

A research group led by Prof.GE Ziyi at the Ningbo Institute of Materials Technology and Engineering(NIMTE)of the Chinese Academy of Sciences,has developed three isomeric bisphosphonate-anchored self-assembled molecules(SAMs),making it possible to achieve high-efficiency and stable inverted perovskite solar cells(PSCs).

Application of EDTMPS as a novel calcite depressant in scheelite flotation

In this study, the innovative use of ethylenediamine tetramethylene phosphonic sodium(EDTMPS) as a calcite depressant in scheelite flotation was investigated by flotation experiments, and its selective depression mechanism was revealed by contact angle measurement, FTIR analysis, Zeta potential test and XPS analysis. The flotation experiment results showed that scheelite and calcite could be efficiently separated under the following conditions: pulp p H=9.5, Na OL concentration of 1.5×10^(-4)mol/L, EDTMPS concentration of 3.0×10^(-5)mol/L, a scheelite concentrate with WO3grade of 65.49%, recovery of 83.29%and separation efficiency of 65.29% could be obtained from the artificially mixed minerals. The analysis results of mineral surface properties demonstrated that EDTMPS was strongly adsorbed onto the calcite surface through the reaction between the phosphonate group and the calcium ions, which hindered Na OL adsorption and increased the hydrophilicity of calcite. However, EDTMPS had weak adsorption strength on the scheelite surface, which didn’t affect further adsorption of Na OL, hence, the scheelite remained hydrophobic. Consequently, the selective adsorption of EDTMPS on the two minerals’ surfaces increased a difference in wettability and thus enabling them to be separated by flotation. Finally, the mechanism model of this flotation separation process was established.

Synthesis of phosphonated graphene oxide by electrochemical exfoliation to enhance the performance and durability of high-temperature proton exchange membrane fuel cells

The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).

Aminated (Cyclopropylmethyl)Phosphonates: Synthesis and Anti-Pancreatic Cancer Activity

Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.

Flotation behavior and adsorption mechanism of(1-hydroxy-2-methyl-2-octenyl) phosphonic acid to cassiterite

The flotation behavior and adsorption mechanism of novel（1-hydroxy-2-methyl-2-octenyl） phosphonic acid（HEPA） to cassiterite were investigated by micro-flotation tests, zeta potential measurements, FTIR determination and density functional theory（DFT） calculation. The flotation results demonstrated that HEPA exhibited superior collecting performance compared with styrene phosphonic acid（SPA）. The cassiterite recovery maintained above 90% over a wide pH range of 2-9 with 50 mg/L HEPA. The results of zeta potential measurement and FTIR detection indicated that the adsorption of HEPA onto cassiterite was mainly attributed to the chemisorption between HEPA monoanions and Sn species on mineral surfaces. The DFT calculation results demonstrated that HEPA monoanions owned higher HOMO energy and exhibited a better affinity to cassiterite than SPA, which provided very clear evidence for the stronger collecting power of HEPA presented in floatation test and zeta potential measurement.

Facile Synthesis and Adsorption Properties of Phosphonated Cellulose Beads for Selective Removal of Low-density Lipoprotein

A novel low-density lipoprotein adsorbent was prepared simply by directly phosphonating porous cellulose beads. Tests in vitro demonstrated that this adsorbent showed quite good adsorption performance for selective removal of low-density lipoprotein from human plasma. The effects of preparation conditions on the lipoprotein sorption properties of the resulted adsorbent were investigated. The adsorption dynamics was also examined.

Enantioselective synthesis of chiral phosphonylated 2,3-dihydrofurans by copper catalyzed asymmetric formal [3+2] cycloaddition of propargylic esters with β-keto phosphonates

Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.

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.

Hydrophobic flocculation flotation of rutile fines in presence of styryl phosphonic acid

The hydrophobic flocculation flotation of rutile fines in the presence of styryl phosphonic acid（SPA） was investigated by flotation tests, zeta-potential measurement, optical microscope observation, laser-based particle size analysis, adsorption measurements and DLVO theory. The flotation tests indicated that rutile fines could be flocculated by SPA, and pH, shear force（stirring speed） and stirring time played significant roles in flocculation. The isoelectric point（IEP） and zeta-potential in whole range all moved to negative values as SPA was added according to the results from zeta-potential measurement. It was demonstrated that the primary reason for above was chemical adsorption. The laser-based particle size results showed the particle size at a stirring speed of 1800 r/min and 1000 mg/L SPA was the largest in all experiments. Furthermore, using the optical microscope observation and flotation tests, it was important for flotation of rutile fines to produce the flocculant. In the light of above-mentioned facts, floc flotation of rutile fines could be induced in the form of chemical adsorption by SPA to increase particle size. The data calculated from DLVO theory also indicated that chemical adsorption was the main reason for the formation of flocculant.

Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts

The exploration of cost-effective non-noble-metal electrocatalysts is highly imperative to replace the state-of-the-art platinum-based catalysts for oxygen reduction reaction(ORR). Here, we prepared cobalt phosphonate-derived N-doped cobalt phosphate/carbon nanotube hybrids(Co Pi C-N/CNTs) by hydrothermal treatment of N-containing cobalt phosphonate and oxidized carbon nanotubes(o-CNT) followed by high-temperature calcination under nitrogen atmosphere. The resultant Co Pi C-N/CNT exhibits a superior electrocatalytic performance for the ORR in alkaline media, which is equal to the commercial Pt/C catalyst in the aspect of half-wave potential, onset potential and diffuse limiting current density. Furthermore, the excellent tolerance to methanol and strong durability outperform those of commercial Pt/C. It is found that cobalt phosphonate-derived N-doped cobalt phosphate and the in-situ formed graphitic carbons play key roles on the activity enhancement. Besides, introducing a suitable amount of CNTs enhances the electronic conductivity and further contributes to the improved ORR performance.

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.

Separation of Eu^3＋ Using a Novel Dispersion Combined Liquid Membrane with P507 in Kerosene as the Carrier

The separation of Eu^3 ＋is studied with a dispersion combined liquid membrane（DCLM）,in which polyvinylidene fluoride membrane（PVDF）is used as the liquid membrane support,dispersion solution containing HCl solution as the stripping solution,and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester（P507）dissolved in kerosene as the membrane solution.The effects of pH value,initial concentration of Eu3 ＋and different ionic strength in the feed phase,volume ratio of membrane solution to stripping solution,concentration of HCl solution, concentration of carrier,different stripping agents in the dispersion phase on the separation are investigated.The optimum condition for separation of Eu3 ＋is that concentration of HCl solution is 4.0 mol·L 1,concentration of carrier is 0.16 mol·L 1,and volume ratio of membrane solution to stripping solution is 30︰30 in the dispersion phase, and pH value is 4.2 in the feed phase.The ionic strength has no significant effect on separation of Eu3 ＋.Under the optimum condition,when the initial concentration of Eu3 ＋is 0.8×10 4mol·L 1,the separation percentage of Eu 3＋is 95.3%during the separation time of 130 min.The kinetic equation is developed in terms of the law of mass diffusion and the theory of interface chemistry.The diffusion coefficient of Eu3 ＋in the membrane and the thickness of diffusion layer between feed phase and membrane phase are obtained and their values are 1.48×10 7m 2·s 1and 36.6μm,respectively.The results obtained are in good agreement with literature data.

Highly efficient production of 2,5-dihydroxymethylfuran from biomass-derived 5-hydroxymethylfurfural over an amorphous and mesoporous zirconium phosphonate catalyst

The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.

Synthesis of N-methylene phosphonic chitosan(NMPCS)and its potential as gene carder

N-Methylene phosphonic chitosan （NMPCS）, an amphiphilic macromolecule with powerful chelating ability of Ca^2＋ ions, was synthesized and characterized. The physicochernical properties of NMPCS and the interactions between NMPCS and plasmid DNA were investigated by FTIR, ^13C NMR, X-ray, agarose gel electrophoresis retardation assay, atomic force microscopy （AFM） and circular dichroism （CD）. The results suggest that at charge ratio 2：1 or above, DNA could be completely entrapped and spherical complexes with mean size of 80-210 nm were formed. Taking HeLa as host cell, luciferase expression mediated by NMPCS improved about 100 times compared to the expression mediated by chitosan.