Deciphering Water Oxidation Catalysts:The Dominant Role of Surface Chemistry over Reconstruction Degree in Activity Promotion

Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has been often correlated with the activity enhancement.Here,a systematic study on the roles of Fe substitution in activation of perovskite LaNiO_(3)is reported.The substituting Fe content influences both current change tendency and surface reconstruction degree.LaNi_(0.9)Fe_(0.1)O_(3)is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_(1-x)Fe_(x)O_(3)(x=0.00,0.10,0.25,0.50,0.75,1.00)series.The reconstructed LaNi_(0.9)Fe_(0.1)O_(3)shows a higher intrinsic activity than most reported NiFe-based catalysts.Besides,density functional theory calculations reveal that Fe substitution can lower the O 2p level,which thus stabilize lattice oxygen in LaNi0.9Fe0.1O3 and ensure its long-term stability.Furthermore,it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree.The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction.This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.

Electrorheological Properties of Rare Earth Oxide and Rare Earth Hydroxide

The electrorheological(ER)behaviors of 31 kinds of ER suspensions,16 kinds of rare earth oxide and 15 kinds of rare earth hydroxide[RE(OH)_(3)]are tested systematically under electric field.The microscopy shows that only Gd_(2)O_(3),Pr6O11 from rare earth oxides and RE(OH)_(3)·nH_(2)O(RE=La,Y,Pr,Gd,Sm,Lu)from rare earth hydroxides dispersed in silicone oil produce fibrous chains in the direction of the ac field vector.The viscosities of ER suspensions with Gd_(2)O_(3),Pr_(6)O_(11),RE(OH)_(3)·nH_(2)O(RE=La,Y,Gd,Pr)dispersed in hydrocarbon oil are determined under different field strength(dc field).The results show that the ER activity of the materials is not influenced by the coordinated water with the rare earth ion,and it is related with the microstructure of the molecule.

Strong metal-support interactions between highly dispersed Cu^(+) species and ceria via mix-MOF pyrolysis toward promoted water-gas shift reaction

The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.

Structure and Electrorheological Performance of Nanosized Y_2O_3-Doped TiO_2 Particle Materials

The nanosized particle materials of doped-TiO_2 with Y_2O_3 were prepared by means of sol-gel technique for use in electrorheological (ER) fluids, and their crystal structures were measured by X-ray diffraction (XRD) analysis. To compare with the pure TiO_2, a distinct enhancement in the shear stress under dc electric field was found by using such materials. This can be explained by the increase of the dielectric loss and dielectric constant at low frequency. The effects of the crystal structure of the particles on the dielectric property and ER performance of materials were investigated.

Preparation and Electrorheological Property of Y_4O(OH)_9(NO_3)-NH_4NO_3 Materials

The new electrorheologicai （ER） material, a particle material composed of Y4O（OH）9（NO3） and NH4NO3, was obtained. They display better ER performance. The shear stress of the suspension of Y4O （OH）9 （NO3） （ NH4NO3 ）2.8 material in dimethyl silicone oil reaches 1469 Pa at an electric field strength （E） of 4.2 kV·mm^-1 and the shear rate （7） of 150 s^-1 The relative shear stress, τ E/τ0（ τE and τ0 are the shear stresses at E = 4.2 and 0 kV·mm^-1 respectively）, is up to 29, which is 19 times that of pure Y2O3 material. The dielectric and conductive property of the materials play important roles in the modification of the ER effect of the particle materials. The researches on these new ER materials are very useful for obtaining a better understanding on the mechanism of the ER effect and finding an ideal ER material.

Minimum Amount of Extracting Solvent of a Separation of Two Rare Earth Components

A significant development in the theory of countercurrent extraction will be presented in this article. New expressions of the term in countercurrent extraction process analysis, “Adjacent Stage Impurity Ratio” (ASIR), are deduced. Furthermore, based on the term together with mass balance and extraction equilibrium, the conditions where a given countercurrent extraction separation operation can have minimum amounts of both extracting solvent and scrubbing agent solution can be estimated, and the equations of the two minimum amounts can be deduced. It was found that the equations for a two-component separation using a single aqueous or organic feed are exactly the same as they appeared in the theory initially established in 1970s. Unlike its earlier version, the present derivation does not involve feed-stage-composition hypothesis, and also has the advantage of dealing with a double-feed system where both aqueous and organic feeds are simultaneously employed whereas the earlier theory can only analyze a separation using a single aqueous or organic feed.

Effect of Y_2(CO_3)_3 and Surfactants on Electrorheological Performance of SiO_2 Particle Materials

The SiO_2 particle material has weak electrorheological (ER) activity. The ER performance of the SiO_2 particles can be ameliorated after adsorbing Y_2(CO_3)_3. In this paper, the effect of Y_2(CO_3)_3 and different surfactants on the ER performance of the SiO_2 particle materials is investigated. The results show that anionic or cationic surfactants maybe enhance the ER activity of SiO_2 material, and nonionic surfactants cannot when surfactants are added during the process of the SiO_2 particle preparation, only the anionic surfactant, AES, can enhance markedly the ER performance of the material. The surface area, pore volume and pore diameter of the particles were measured. The effect of Y_2(CO_3)_3 and the surfactants on the microstructure of SiO_2 materials and the relationship between ER effect and the microstructure are described.

Preparation and Electrorheological Performance of SiO_2 Particle Materials Adsorbed with YF_3, Y_2(CO_3)_3, Y_2(C_2O_4)_3 or YPO_4

The SiO 2 adsorbing YF 3, Y 2(CO 3) 3, Y 2(C 2O 4) 3 and YPO 4, respectively, formed four systems of particle materials: SiO 2·YF 3, SiO 2·Y 2(CO 3) 3 , SiO 2·Y 2(C 2O 4) 3 and SiO 2·YPO 4. The electrorheological(ER) behavior of the electrorheological fluids (ERF) prepared by dispersing them in silicone oil was tested at 20 ℃ under d.c. field. The results show that the system of SiO 2·YF 3 does not display ER activity, and the ER performance of the particle materials of SiO 2·Y 2(CO 3) 3 is the best among them. The shearing stress of ERF with SiO 2·Y 2(CO 3) 3 particles is 1.644 KPa and the relative viscosity η r(=η E/η 0) is 20.3 (under field strength E=4200 V·mm -1) while the adsorbed content of Y 2(CO 3) 3 in the SiO 2 particle materials is 12.4%(mass fraction).

Emission of Rare Earth Complex Tb_(0.5)Eu_(0.5) (asprin)_3phen

The coprecipitate Tb 0.5 Eu 0.5 3phen was synthesized. By doping the rare earth complex into polymer PVK, the EL device was fabricated with the structure of ITO/PVK∶RE/PBD/Al. Compared with the device using PVK/Eu(asprin) 3phen blend as the light emitting layer, the emission of Eu 3+ in the PVK/Tb 0.5 Eu 0.5 (asprin) 3 phen blend is greatly enhanced along with the quenching of the emission of PVK.

Luminescence and Preparation of LED Phosphor Ca_8Mg(SiO_4)_4Cl_2∶Eu^(2+)

Calcium magnesium chlorosilicate doped by europium, Ca8Mg（SiO4）4Cl2： Eu^2＋, was prepared by the solid state reaction at high temperature. The compound obtained is pure Ca8Mg（SiO4）4Cl2 phase with cubic structure. Its average particle size is 5 μm, and it has good dispersity and morphological form. The excitation spectrum of Ca8Mg（SiO4）4Cl2： Eu^2＋ is a wide band, which covers from 270 to 480 nm. The emission spectrum is also a wide band peaked at 510 nm. The luminescent intensity reaches to the maximum when the concentration of Eu^2 ＋ is 2%. The wavelength of emission and excitation of the phosphor with various Eu^2 ＋ contents keeps constant. This spectrum range matches violet and blue LED chips very well, and its strong luminescence intensity is suitable for a green phosphor of tricolor phosphor of white light LED.

Synthesis,Characterization and Fluorescence Properties of Europium,Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen) L3·1/2H2O; Tb (phen) L3·H2O and Tb0.5 RE0.5(Phen)L3·1/2H2O. (RE = Y3+, La3+ and Gd3+; L = biphenyl 4-carboxylic acid; phen = o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE (III ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 + is raised by inert fluorescent rare earth ions (Y3+ , Gd3+ and La3+ ), but in Tb3+ hetero-nuclear rare earth complexes the intensity of Tb3+ ions are quenched by the inert fluorescent rare earth ions.

Preparation of ceria with large particle size and high appearance density

Cerium is one of the most abundant rare earth elements in both bastnasite and monazite. Ceria has been widely used in optical, catalytic, electrolyte, and sensor materials, with unique performances. With the development of functional materials, great interest has been focused on the synthesis and characterization of specific fine/mesoporous ceria powder. In this study, the modified precipitation and recrystallization processes combined with a controlled calcination process for fabricating the ceria with large particle size and high appearance density was reported. During precipitation, a certain amount of mineral acid such as nitric acid served as an additive, to adjust the precipitation and crystallization processes of cerium oxalates. An appropriate acidic condition could lead the process into the Oswald ripening stage and made the particles become bigger. Thus, the appearance density of powder was increased. The optimized conditions, such as the temperature, feeding speed, type and concentration of mineral acids, and the concentration of cerium-contained stock solution, were investigated and evaluated.

Metal cyanamides: Open-framework structure and energy conversion/storage applications

Metal cyanamides are an emerging class of functional materials with potential applications in sustainable energy conversion and storage technologies such as catalysis,supercapacitors,photoluminescence and next-gen batteries.The[NCN]^(2-)as the anion,which is isolobal with[O]^(2-)endows metal cyanamides with similar physicochemical properties as oxides and chalcogenides.Whereas the unique quasI-linear structure and electronic resonance between[N=C=N]^(2-)and[N-C≡N]^(2-)of[NCN]entity bring out superior properties beyond oxides and chalcogenides.In this review,we present research status,challenges,and the recent striking progress on the metal cyanamides in the synthesis and applications.Specifically,the characteristic structures,physicochemical properties,synthetic methods with corresponding merits/demerits and latest applications in energy conversion and storage of cyanamides are summarized.The detailed outlooks for the new compounds design,morphology manipulation and potential applications are also exhibited.

Study on Band Structure of YbB_6 and Analysis of Its Optical Conductivity Spectrum

The electronic structure of YbB6 crystal was studied by means of density functional （GGA ＋ U） method. The calculations were performed by FLAPW method. The high accurate band structure was achieved. The correlation between the feature of the band structure and the Yb-B6 bonding in YbB6 was analyzed. On this basis, some optical constants of YbB6 such as reflectivity, dielectric function, optical conductivity, and energy-loss function were calculated. The results are in good agreement with the experiments. The real part of the optical conductivity spectrum and the energy-loss function spectrum were analyzed in detail. The assignments of the spectra were carried out to correlate the spectral peaks with the interband electronic transitions, which justify the reasonable part of previous empirical assignments and renew the missed or incorrect ones.

Preparation and Electrorheological Property of NaNO_3-Doped Y_2O_3 Material

A new class of electrorheological （ER） material using rare earth （RE = Y） oxide as the substrate, NaNO3- doped Y2O3 materials, were synthesized using Na2CO3 and Y（NO3）3 as starting materials. Their ER performance, dielectric property, and crystal structure were studied. The results show that doping NaNO3 can markedly enhance the ER activity of the Y2O3 material. For the suspensions of these materials in dimethyl silicone oil, a clear dependence of the shear stress on the doping degree of NANO3 was observed, and the optimal value of Na/Y molar ratio of 0.6 in doping degree was discovered, the relative viscosity ηr（ ηE/η0, E = 4.2 kV·mm^-1） of the suspensions is nine times higher than that of pure Y2O3 material. The new results of the relationship between ER effect and the microstructure were obtained, which are helpful for further understanding the mechanism of ER effect and synthesizing a good ER material.

Peanut-chocolate-ball-inspired construction of the interface engineering between CdS and intergrown Cd:Boosting both the photocatalytic activity and photocorrosion resistance

Interface engineering can improve the charge separation efficiency and inhibit photocorrosion is an emerging direction of developing more efficient and cost-effective photocatalytic systems.Herein,we report the sulfur-confined intimate Cd S intergrown Cd(Cd S/Cd)Ohmic junction(peanut-chocolate-ball like)for high-efficient H2production with superior anti-photocorrosion ability,which was fabricated from in-situ photoreduction of CdS intergrown Cd2SO4(OH)2(CdS/Cd2SO4(OH)2)prepared through a facile space-controlled-solvothermal method.The ratios of CdS/Cd can be effectively controlled by tunning that of CdS/Cd2SO4(OH)2which were prepared by adjusting the volume of reaction liquid and the remaining space of the reactor.Experiments investigations and density functional theory(DFT)calculations reveal that the Cd S intergrown Cd Ohmic junction interfaces(with appropriate content Cd intergrown on Cd S(19.54 wt%))are beneficial in facilitating the transfer of photogenerated electrons by constructing an interfacial electric field and forming sulfur-confined structures for preventing the positive holes(h+)oxidize the Cd S.This contributes to a high photocatalytic H2production activity of 95.40μmol h-1(about 32.3 times higher than bare Cd S)and possesses outstanding photocatalytic stability over 205 h,much longer than most Cd S-based photocatalysts previously reported.The interface engineering design inspired by the structure of peanut-chocolate-ball can greatly promote the future development of catalytic systems for wider application.

The influence of different monodentate P-ligand mixtures on Rh-catalyzed 1-butene hydroformylation

Four monodentate P-ligands and their mixtures（six groups of double-ligand systems,four groups of triple-ligand systems and one group of tetra-ligand system）were used with Rh（acac）（CO）2（acac=acetylacetonate）or Rh（acac）CO（PPh3）as the catalyst in the hydroformylation reaction of 1-butene.It was found that different Rh catalysts showed little difference in the catalysis performance.The general order of catalysis performance is doubleligand system 〉 single-ligand system〉triple-ligand system 〉 tetra-ligand system.Some synergistic effect in the double-ligand system was detected which needs a further investigation.

Electronic structure and spatial inhomogeneity of iron-based superconductor FeS

Iron-based superconductor family FeX(X=S,Se,Te)has been one of the research foci in physics and material science due to their record-breaking superconducting temperature(FeSe film)and rich physical phenomena.Recently,FeS,the least studied Fe X compound(due to the difficulty in synthesizing high quality macroscopic crystals)attracted much attention because of its puzzling superconducting pairing symmetry.In this work,combining scanning tunneling microscopy and angle resolved photoemission spectroscopy(ARPES)with sub-micron spatial resolution,we investigate the intrinsic electronic structures of superconducting FeS from individual single crystalline domains.Unlike FeTe or FeSe,FeS remains identical tetragonal structure from room temperature down to 5 K,and the band structures observed can be well reproduced by our ab-initio calculations.Remarkably,mixed with the 1×1 tetragonal metallic phase,we also observe the coexistence of √5×√5 reconstructed insulating phase in the crystal,which not only helps explain the unusual properties of FeS,but also demonstrates the importance of using spatially resolved experimental tools in the study of this compound.

Photoluminescent and Electroluminescent Properties of Ligand Emitting Y^(3+), La^(3+), Gd^(3+) and Lu^(3+) Complexes

The photoluminescent (PL) and electroluminescent (EL) properties of a series of ligand emitting rare earth complexes (including Y^(3+), La^(3+), Gd^(3+) and Lu^(3+)) were systematically studied. These complexes have the same anionic ligand, 1-phenyl-3-methyl-4-isobutyryl-5-pyrazoloneate (PMIP), and three neutral ligands, triphenyl phosphine oxide (TPPO), 2, 2′-dipyridine (Bipy) and phenanthroline (Phen). Measured with 60 nm thin film of these complexes vaporized in vacuum on quartz substrates, a good regularity in the PL properties was observed. For rational comparison, the same structural EL devices based on these complexes, ITO/PVK (40 nm)/the complex (80 nm)/Mg: Ag (200 nm)/Ag (100 nm), were fabricated. Excluding the exciplex emission happens, the EL luminance usually increases with the increasing of PL efficiency.

Effects of Synthetic Parameters in Pechini Method on the Formation and Properties of (ZrO_2)_(0.92)(Sc_2O_3)_(0.08) Solid Solution

Homogeneous (ZrO_2)_(0.92)(Sc_2O_3)_(0.08) solid solution in fluorite cubic structure was prepared from the gels with altered molar ratios of citric acid (CA) to metal ions (M) and ethylene glycol (EG) via a polymerization route (Pechini method). Due to the enhanced chemical homogeneity (high level of mixing of metal ions and ligands) in the polymeric gels, Sc-doped zirconia can be crystallized at temperatures as low as 400 ℃. During the evolution from amorphous gel to the crystallized (ZrO_2)_(0.92)(Sc_2O_3)_(0.08) fine powder, the bonding nature between carboxylate groups and Zr/Sc cations changed: unidentate→bridging→ionic upon calcination. The molar ratios of CA/M (1～4) and CA/EG (0.2～4) were demonstrated to affect the thermal behavior of the gels and thus the particle properties of the derived nanoparticulate oxide powders (including particle size and surface area). The as-sintered sample compacted from the nanosized powders prepared by calcining the gel with the highest content of organics (CA/M=4 and CA/EG=0.2) exhibited the best sinterability and the highest oxide ion conductivity.