Exceptional Performance of 3D Additive Manufactured NiFe Phosphite Oxyhydroxide Hollow Tubular Lattice Plastic Electrode for Large-Current-Density Water Oxidization

In this article,we report a 3D NiFe phosphite oxyhydroxide plastic electrode using high-resolution digital light processing(DLP)3D-printing technology via induced chemical deposition method.The as-prepared 3D plastic electrode exhibits no template requirement,freedom design,low-cost,robust,anticorrosion,lightweight,and micro-nano porous characteristics.It can be drawn to the conclusion that highly oriented open-porous 3D geometry structure will be beneficial for improving surface catalytic active area,wetting performance,and reaction–diffusion dynamics of plastic electrodes for oxygen evolution reaction(OER)catalysis process.Density functional theory(DFT)calculation interprets the origin of high activity of NiFe(PO_(3))O(OH)and demonstrates that the implantation of the–PO_(3)can effectively bind the 3d orbital of Ni in NiFe(PO_(3))O(OH),lead to the weak adsorption of intermediate,make electron more active to improve the conductivity,thereby lowing the transform free energy of*O to*OOH.The water oxidization performance of as-prepared 3D NiFe(PO_(3))O(OH)hollow tubular(HT)lattice plastic electrode has almost reached the state-of-the-art level compared with the as-reported large-current-density catalysts or 3D additive manufactured plastic/metal-based electrodes,especially for high current OER electrodes.This work breaks through the bottleneck that plagues the performance improvement of low-cost high-current electrodes.

Phosphite Ligand Modified Supported Rhodium Catalyst for Hydroformylation of Internal Olefins to Linear Aldehydes

A phosphite ligand modified heterogeneous catalyst was developed for the hydroformylation of internal olefins to linear aldehydes, which showed a high activity and high regioselectivity and could be separated easily by filtration after reaction in an autoclave. Three nanoporous silica sieves were used to investigate the influence of pore structure and shape selective performance of support on the regioselectivity to the linear products.

Metabolomics Profile of Potato Tubers after Phosphite Treatment

Phosphite (Phi)-based fungicides are used to control the oomycete Phytophthora infestans which causes late blight disease, the most devastating disease in potatoes. In order to examine the effects of Phi-based fungicides on potato tubers through foliar or post-harvest application, a metabolite profiling approach based on gas chromatography coupled to mass spectrometry (GC-MS) has been established. A total of 132 metabolites were detected using the GC-MS approach. Among these, 34 metabolites were identified after normalization and annotated with a compound name with standard mass spectral library. Metabolomic analysis of Phi-treated plants showed significant differences in the levels of many metabolites especially amino acids. Multivariate statistical approaches, such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA), were employed to explore the relationships between metabolites to detect group differences. A good discrimination between the control and the Phi-treated plants was observed, which demonstrated that significant changes in the metabolite profile have been caused by the two different Phi applications (foliar or post-harvest). This finding suggests that the alteration of specific metabolite levels by accumulation of Phi can lead to resistance against the pathogen.

Synthesis and Characterization of Two New Organically Templated Open-framework Uranium Phosphites

Two organically templated uranium phosphites, （C4H12N）（UO2）（HPO3）（NO3） （Mr = 486.16） 1 and （C16H36N）2（UO2）2（H2PO3）2（HPO3）（NO3）2 （Mr= 1390.95） 2, were prepared by evaporation from aqueous solution of uranyl nitrate, phosphite acid and their respective organic ammonium hydroxids. Their structures were determined by single-crystal X-ray diffraction and further characterized by infrared and fluorescence spectroscopy. In 1, pentagonal [UO7] bipyramids share comers with three [HPO3]2- tetrahedra and one edge with a [NO3]- anion to form [（UO2）- （HPO3）（NO3）]^- ladder-like chains parallel to the b axis. The structure of 2 is also based upon one-dimensional anionic [（UO2）2（H2PO3）2（HPO3）（NO3）2]2-chains of comer-sharing penta- gonal [UOT] bipyramids with [H2PO3]- and [HPO3] tetrahedra, which is still unknown in structural chemistry of uranium so far. Crystal data for 1： monoclinic, space group C2/m, a = 21.808（7）, b = 6.9605（15）, c = 8.357（2） A, β = 98.327（15）°, V= 1255.2（6） A^3, Z = 4, Dc = 2.573 g/cm^3, F（000） = 888, μ = 13.086 mm^-1 the final R = 0.0418 and wR = 0.0906 （I 〉 2σ（I））; and those for 2： monoclinic, space group C2/c, a = 36.4549（8）, b = 14.5296（11）, c = 20.8253（11） A, β = 101.7440（8）°, V= 10799.7（10） A3, Z = 8, Dc= 1.711 g/cm^3, F（000） = 5424,μ = 6.144 mm^-1, the final R= 0.0368 and wR= 0.0865 （I〉 2σ（I））.

Hydroformylation of methyl-3-pentenoate over a phosphite ligand modified Rh/SiO_2 catalyst

A phosphite ligand modified Rh/SiO2 catalyst has been developed for hydroformylation of internal olefins to linear aldehydes, which showed high activity and regioselectivity and could be separated easily by filtration after reaction in an autoclave. Effects of reaction temperature and syngas pressure on the performances of the catalyst in the reaction were also investigated.

An efficient method for the synthesis of dialkyl chlorophosphates from trialkyl phosphites using bis(trichloromethyl)carbonate

A mild and simple method for the synthesis of dialkyl chlorophosphates is described, bis（trichloromethyl） carbonate （BTC） is used as the effective reagent for the conversion of dialkyl phosphites to their corresponding dialkyl chlorophosphates under mild conditions.

Syntheses, Structures, and Luminescence Properties of Two New Open-framework Zinc Phosphites Based on 1,2,4-Triazole Derivatives

With 1,2,4-triazole derivatives as structure directing agents, two new openframework zinc phosphites, [Zn（atrz）（HPO3）]n（1） and [Zn（dmatrz）（HPO3）]n（2）（atrz = 4-amino-1,2,4-triazole, dmatrz = 4-amino-3,5-dimethyl-1,2,4-triazole） have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder and single-crystal X-ray diffractions. Both compounds are isostructure and crystallize in the P21/c space group of monoclinic system. Compound 1： a = 9.629（1）, b = 7.384（1）, c = 10.274（1） A, β = 110.729（3）°, V = 683.26（2） A^3, Z = 4, Mr = 229.44, Dc = 2.230 g/cm^3, F（000） = 456, S = 1.10, μ = 3.79 mm^（–1）, R = 0.0181 and w R = 0.0466 for 1121 observed reflections（（40） 〉 2s（（40）））. Compound 2： a = 10.786（2）, b = 8.921（1）, c = 9.749（1） A, β = 107.3°, V = 895.6（3） A^3, Z = 4, Mr = 257.49, Dc = 1.910 g/cm^3, F（000） = 520, S = 1.00, μ = 2.90 mm^（–1）, R = 0.018 and wR = 0.051 for 1581 observed reflections（（40） 〉 2s（（40）））. Both compounds are built up into 4.8-net 2D open-frameworks of vertex-linked Zn O4 and HPO3 units（3.57 × 4.53 A^2 for 1 and 4.43 × 5.90 A^2 for 2）. The structures consist of left-, right-handed helical chains that are connected through oxygen atoms to form an undulated 2D sheet stack, which can be topologically regarded as 4.8~2 nets. Solid-state luminescence properties and thermo gravimetric analyses of these two compounds were investigated, respectively.

One-pot-synthesis of novel cinchonine-based phosphites

Cinchonine was employed as backbone for the synthesis of novel phosphite compounds with diol substituents. These monophosphinites were provided in one pot with the yields ranged from 63% to 75%. Their structures were confirmed by NMR spectroscopy and HRMS. C 2009 Sheng Yong Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

A New Convenient Method for the Resolution of 1, 1'-Binaphthalene-2, 2'-diol Via a Phosphite Using (-)-Menthol as Resolving Agent

Menthol reacts with phosphorus trichloride to afford menthyl phosphorodichloridite 2, which further reacts with racemic 1, 1-binaphthalene-2, 2-diol to give phosphite (+)-3 in the presence of triethylamine. (+)-3 can be easily separated by fractional crystallization to form the crystal (+)-(S)-3 and the mother liquor (-)-(R)-3. Then both the crystal and the mother liquor are treated with AcOH-H2O to obtain enantiomeric pure (-)-(S)-1 and (+)-(R)-1 respectively, with enantiomeric excess up to 99.7%.

Synthesis and Structure of an Organo-templated Oxouranium Phosphite

A novel layered oxouranium phosphite open-structure [（C10H24N2）（H2O）][（UO2）2（HPO3）3]（denoted as TJPU-8,TJPU=Tianjin Polytechnic University） was hydrothermally synthesized with isophorondiamine（IPDA） as the template.Single crystal structure refinement disclosed that TJPU-8 crystallized in the monoclinic space group P21c with cell parameters a=1.8346（9） nm,b=0.6734（1） nm,c=2.0639（0） nm,β=114.61（5）°,V=2.3182（8） nm3,Z=2.TJPU-8 was constructed by UO7 monomer,U2O12 dimer and HPO3 groups.The monomeric UO7 or dimeric U2O12 was connected by HPO3 groups to form two types of 4-ring chains.An undulating sheet was then generated by connecting these two types of chains via HPO3 bridges.The layer structure formed by stacking the sheets along the a direction via the strong H-bonds of organoamine cations and water molecules intercalated in the interlayer spaces with the framework oxygen atoms.Although a mixture of cis-and trans-IPDA was used,only cis-IPDA served as the template.A typical green light emission of TJPU-8 is observed when excited by 266 nm laser.

THE REACTION OF SUBSTITUTED PHENOXY ACETYL CHLORIDE WITH TRIMETHYL PHOSPHITE

Substituted phenoxy acetyl chloride reacted with trimethyl phosphite to form an unexpected substituted phenoxy acetic acid ester, confirmed by ~1HNMR, IR and MS. The mechanism suggested is different from that of Arbuzov reaction.

New 3D Framework Vanadium(Ⅲ) Phosphite with One-dimensional 4,12-Member Ring Channels

A new vanadium（Ⅲ） phosphite,V2（HPO3）3（1）,was synthesized hydrothermally with V2O5,H3PO3 as reactants,1,6-diaminopropane（1,6-HAD） as the structure-directing agent and characterized by single crystal X-ray diffraction,powder X-ray diffraction,IR spectroscopy,TGA,ICP-AES and elemental analyses.Single-crystal X-ray diffraction analysis reveals that compound 1 crystallized in the P6（3）/m hexagonal space group with the unit-cell parameters：a=0.80436（10） nm,c=0.73972（2） nm,V=0.41447（13） nm^3,Z=4.The construction of 3D framework structure of compound 1 may be viewed as the assembly of V2O9 dimers and HPO3 pseudo-pyramids which lead to form the one-dimensional 4,12-member ring channels along the [001] direction.

The Synthesis of Glycosyl Phosphite-Pt(II) Complexes

Ethylene glycol phosphorochloridite 1 or catechol phosphorochloridite 2 reacted with isopropylidene derivatives of D-glucose, D-galactose, D-mannose and D-fructose, a series of glycosyl phosphites were obtained. These glycosyl phosphites form optically active complexes with simple Pt (膊) salts. Pt (II) is coordinated to the phosphorus atom, most of the metal complexes are quite stable.

Synthesis and Diastereomeric Analysis of Uridine 2’,3’-Cyclic Phosphite

Uridine 2’,3’-cyclic phosphite has been synthesized and the diastereomers were analysed by 2D NMR technique to assign the configuration

The Activity and Theoretical Interpretation of Role of Trimethyl Phosphite Modified HZSM-5 Zeolite

The catalytic activity of trimethyl phosphite modified HZSM-5 zeolite and un-modified HZSM-5zeolite treated with 100% steam at 673,773,873,973 and 1073K, respectively, were investigated using heptanecracking as a probe reaction. The results showed that the heptane conversion of both trimethyl phosphitetreated samples and un-phosphated samples decreased with an increase in treating temperature, but trimethylphosphite modified samples showed higher activity in comparison with the un-modified samples, which weresteam-treated at a higher temperature. The results were firstly elucidated by the model cluster method andcomputational quantum chemistry method. Full optimization and frequency analysis of all cluster model havebeen carried out using the Gaussian 94 software-package with the PM 3 semi-empirical method performed onsmall cluster models. The computational results showed that the dealumination of trimethyl phosphite modi-fied zeolite model cluster was more difficult than that of un-modified zeolite model cluster when they weretreated with steam while investigating the heat of reaction.

Synthesis,Characterization and Magnetic Properties of a New Manganese(Ⅱ) Phosphite

A new manganese（Ⅱ） phosphite,Mn 2 F2（HPO3）（1）,was synthesized with tetraethylene pentamine as structure directing agent under hydrothermal conditions.The as-synthesized product was characterized by single crystal X-ray diffraction,powder X-ray diffraction,infrared（IR）,UV-Vis spectrum,thermogravimetric analysis（TGA）,inductive coupled plasma-atomic emission spectroscopy（ICP-AES）,elemental analyses and magnetic susceptibility measurement.Single crystal X-ray diffraction analysis reveals that compound 1 crystallized in the orthorhombic space group Pnma,with a=0.75667（15） nm,b=1.0247（2） nm,c=0.55432（11） nm,V=0.42980（15） nm ^3,Z=4.The 3D compact framework of compound 1 was built up by the Mn2O6F4 dimers and HPO3 pseudo-pyramids.Compound 1,a new metal-rich manganese phosphite,shows a high thermal stability limit of 550 ℃.Magnetic measurement indicates that compound 1 exhibits the global antiferromagnetic interactions with a ferromagnetic transition at 28 K.

A Novel Synthesis of Methyl 4, 6-O-Benzylidene-α-D-Glucopyranoside 2, 3-Cyclic Phosphite Ethyl Ester

A new compound. methyl 4. 6-O-benzylidene-a-D-glucopyranoside 2. 3-cyclicphosphite ethyl ester was synthesized via the reaction of methyl 4. 6-O-benzylidene-a-D-glucopyranoside and ethyl dichlorophosphite. Its structure was confirmed by NMR and MSspectral methods.

ONE'POT REACTION OF TRIVALENTPHOSPHORUS COMPOUNDS (Ⅰ)——A NOVEL ONE-STEP REACTION OF ADDITION,REDUCTION AND CYCLIZATION OF SUBSTITUTED β-NITROSTYRENE WITH O,O-DIALKYL PHOSPHITES

<正> In this paper the reaction of substituted β-nitrostyrene with O,O-dialkyl phosphite under cocatalysis of trimethylsilyl chloride （TMS-C1） and triethylamine （or other acidbinding agent） has been first studied and the new cyclization reaction leading to the formation of product Ⅱ, as a new class of derivatives of 1-hydroxyindoles, difficultly accessible or inaccessible with usual methods has been observed. In the related reaction it is surprising that when the Arbuzov rearrangement occurs under mild conditions, the addition, reduction and cyclization as a one-pot reaction take place simultaneously with the formation of products Ⅰ, Ⅱ, Ⅲ. By controlling the reaction conditions the products were formed almost in specificity, and thus the most interesting cyclic products Ⅱa-hcontaining phosphorus-carbon bond were obtained. Their structures were confirmed by elemental analysis, IR,1H or31p NMR and MS spectra. The crystal structure of representative compound Ⅱhwas determined by X-ray diffract

Asymmetric Pudovik Reaction of Chiral Fluoroalkyl α,β-Unsaturated Ketimines and Diphenyl Phosphite

The asymmetric Pudovik reaction of chiral fluoroalkyl α,β-unsaturated ketimines derivated from(R)-tert-butanesulfinamide and diphenyl phosphite was achieved in the presence of Rb2CO3 at room temperature.A series of fluoroalkylated α-amino phosphonates were prepared in good yields with high diastereoselectivities.

Synthesis of novel cyclohexanediol-derived chiral phosphite ligands and their application in the Cu-catalyzed conjugate addition of organozinc to cyclic enones

A series of novel chiral diphosphite ligands have been synthesized from（1R,2R）-trans-1,2-cyclohexanediol,（1S,2S）-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[（R）-1,10-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand（1R,2R）-bis[（R）-1,1＇-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a＇ derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.