Insights into facet-dependent reactivity of CuO–CeO2 nanocubes and nanorods as catalysts for CO oxidation reaction

Copper–ceria(Cu O–CeO2) catalysts have been known to be very effective for the oxidation of CO, and their chemical behavior has been extensively studied during the last decades. However, the effect of different CeO2 crystal surfaces on the catalytic activity of Cu O–CeO2 for the oxidation of CO is still unclear and should be further elucidated. In this study, we deposited 1 wt% Cu on mostly {100}-exposed CeO2 nanocubes(1 Cu Ce NC) and mostly {110}-exposed CeO2 nanorods(1 Cu Ce NR), respectively. Both 1 Cu Ce NC and 1 Cu Ce NR have been used as catalysts for the oxidation of CO and achieved 100% and 50% CO conversion at 130 ℃, respectively. The differences in the catalytic activity of 1 Cu Ce NC and 1 Cu Ce NR were analyzed using temperature-programmed reduction of H2 and temperature-programmed desorption of CO techniques. The results confirmed the excellent reducibility of the 1 Cu Ce NC catalyst, which was attributed to the weak interactions between Cu and the CeO2 support. Moreover, in situ diffuse reflectance infrared Fourier-transform spectroscopy studies indicated that the {100} planes of 1 Cu Ce NC facilitated the generation of active Cu(I) sites, which resulted in the formation of highly reactive Cu(I)-CO species during the oxidation of CO. Both the excellent redox properties and effective CO adsorption capacity of the 1 Cu Ce NC catalyst increased its catalytic reactivity.

Purification and characterization of Al_(13) species in coagulant polyaluminum chloride

Nano-Al13 was separated and purified by four methods to investigate its characteristic, and was analyzed by Al-Ferron timed complexation spectrophotometer, ^27Al-NMR （nuclear magnetic resonance）, and transmission electron microscopy （TEM）. Coagulation efficiency of nano-Al13, polyaluminum chloride （PAC）, and AlCl3 in synthetic water were also investigated by jar test. The dynamic process and aggregation state of kaolin suspensions coagulating with nano-Al13, PAC, and AlCl3 were also investigated. The experimental results indicated that the efficiency of gel column chromatography method was the highest for separating PAC solution with low Al concentration. Ethanol and acetone method was simple and could separated PAC solution with different Al concentrations, while silicon alkylation white block column chromatography method could separate PAC solution only with low Al concentration. The SO4^2-/Ba^2＋ displacement method could separate PAC solution with high Al concentration, but extra inorganic cation and anion could be introduced into the solution during the separation. The coagulation efficiency and dynamic experimental results showed that nano- Al13 with a high positive-charged species was the main species of electric neutralization in coagulation process, and it could reduce the turbidity and increase the effective particles collision rate efficiently in coagulation process. Its coagulation speed and the particle size of coagulant formed were of greatest value in this study.

N-doped carbon nanotubes formed in a wide range of temperature and ramping rate for fast sodium storage

Herein,nickel@nitrogen-doped carbon nanotubes(Ni@NCNTs)are prepared by a simple and reliable method with Ni-based complex as single-source precursor.Significantly,the formation of CNTs is not susceptible to the calcination temperature and ramping rate and Ni@NCNTs can be attained from 430 to 900℃in an inert atmosphere.Then they are the first time to be applied as the anode material for sodium-ion batteries.The presence of Ni nanoparticles(NPs)facilitates the solid electrolyte interface film over the anode surface and improves the capacity retention of the host material,especially at the high rates.Furthermore,Na+diffusion is reinforced after the introduction of Ni NPs.Ni@NCNTs obtained at 500℃(Ni@NCNTs-500)exhibit the best capacity retention and rate capability.Kinetics analyses demonstrate the faster electron transportation and ion diffusion than others prepared at other temperatures.The surficial capacitance storage favors the fast electrochemistry kinetics.It delivers a high specific capacity(192 mA h g^−1 at 0.5 A g^−1),excellent cycling stability(103 mA h g^−1 after 10,000 cycles at 10 A g^−1),and outstanding high-rate capability up to 20 A g^−1(118 mA h g^−1).The related full cells confirm a high energy density of 140 Wh kg^−1 at 38.16 W kg^−1 and 44.27 W h kg^−1 at 762 W kg^−1.

Catalytic conversion of lignocellulosic biomass into chemicals and fuels

In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock.This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels.Following a brief introduction on the structure,major resources and pretreatment methods of lignocellulosic biomass,the catalytic conversion of three main components,i.e.,cellulose,hemicellulose and lignin,into various compounds are comprehensively discussed.Either in separate steps or in one-pot,cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF,furfural,polyols,and organic acids,or even nitrogen-containing chemicals such as amino acids.On the other hand,lignin is first depolymerized into phenols,catechols,guaiacols,aldehydes and ketones,and then further transformed into hydrocarbon fuels,bioplastic precursors and bioactive compounds.The review then introduces the transformations of whole biomass via catalytic gasification,catalytic pyrolysis,as well as emerging strategies.Finally,opportunities,challenges and prospective of woody biomass valorization are highlighted.

Synthesis and characterization of cerium-modified cubic mesoporous silica

The cerium-modified cubic mobil composition of matters 48 （MCM-48） molecular sieves were synthesized using cetyltrimethylammonium bromide （CTAB） as templates at low molar ratio of surfactant to inorganic precursor. X-ray diffraction （XRD） and transmission electron microscopy （TEM） results show that the well-ordered cubic mesostructure was obtained when the Ce/Si molar ratio is less than 0.05. With the increase of Ce/Si molar ratio, the increase of unit cell parameters and the change of Fourier transform infrared spectroscopy （FTIR） provide powerful evidences for the incorporation of cerium in the framework of mesoporous molecular sieves. Nitrogen sorption data indicate that the Brunauer-Emmett-Teller （BET） surface area and the average pore diameter of Ce（Ⅲ）-MCM-48 are 1288 m 2·g -1 and 4.2 nm, and those of Ce（Ⅳ）-MCM-48 are 1228 m 2·g -1 and 3.7 nm, respectively. Diffuse reflectance UV-visible （UV-vis） spectroscopy confirms the presence of Ce（Ⅲ） in the octahedral position and Ce（Ⅳ） in the fluorite structure. X-ray photoelectron spectroscopy （XPS） studies further reveal that Ce（Ⅲ） and Ce（Ⅳ） coexist in the framework of mesoporous molecular sieves.

Heterotactic Enthalpic Interactions of L-Arginine with 2,2,2-Trifluoroethanol in Aqueous Solutions at 298.15, 303.15 and 310.15 K

The enthalpies of mixing of L-arginine with 2,2,2-trifluoroethanol and their respective enthalpies of dilu- tion in aqueous solutions at 298.15, 303.15 and 310.15 K were determined as a function of the mole fraction by flow microcalorimetric measurement. These experimental results were analyzed to obtain heterotactic enthalpic interaction coeffieients（hxy , hxy , hxy） according to the McMillan-Mayer theory. The hxy coefficients between L-arginine molecule studied and 2,2,2-trifluoroethanol molecule in aqueous solutions at 298.15, 303.15 and 310.15 K were found to be all negative. The results were discussed in terms of solute-solute interaction and solute-solvent interaction.

Synthesis and characteristic of double hydrophilic block copolymer with amine pendant chains

Novel double hydrophilic block copolymers with amine pendant chains were synthesized by polymerization of 4-vinyl benzylamine hydrochloric salt using 4,4′-azo-bis[4-cyanopentanoate poly（ethylene glycol） ester] as macroazoinitiator. The structures of the copolymers were characterized by ^1H NMR, FTIR spectra and acid-base titration, GPC-MALS techniques.

Understanding electrolyte salt chemistry for advanced potassium storage performances of transition-metal sulfides

Molybdenum disulfide/carbon nanotubes assembled by ultrathin nanosheets are synthesized to illustrate the electrolyte salt chemistry via potassium bis-(fluorosulfonyl)imide(KFSI)versus potassium hexafluorophosphate(KPF6).Compared to the case of KPF6,the electrochemical performances using KFSI as the electrolyte salt are greatly improved:~275 mAh g^(−1) after 15,000 cycles at 1 A g^(−1),or~172 mAh g^(−1) even at 40 A g^(−1).These results represent one of the best performances for the reported anode materials.The enhanced performances could be attributed to the FSI-induced changes in the solvate structures,that is,a large solvation energy,a high lowest unoccupied mole cular orbital,and a small bonding dissociation energy of S-F.In this case,a uniform and robust solid-electrolyte interphase(SEI)is produced,improving the mechanical properties and the interface integrity.Then,the uncontrollable fracture and repeated growth of SEI,which always lead to the dissolution of sulfur species and the blockage of charge transfer in the case of KPF6,are well inhibited.This similar enhancement works for other sulfides by KFSI,demonstrating the general importance of this electrolyte salt chemistry.

Versatile MXene Gels Assisted by Brief and Low‑Strength Centrifugation

Due to the mutual repulsion between their hydrophilic surface terminations and the high surface energy facilitating their ran-dom restacking,2D MXene nanosheets usually cannot self-assemble into 3D macroscopic gels with various applications in the absence of proper linking agents.In this work,a rapid spontaneous gelation of Ti3C2Tx MXene with a very low dispersion concentration of 0.5 mg mL^(-1) into multifunctional architectures under moderate centrifugation is illustrated.The as-prepared MXene gels exhibit reconfigurable internal structures and tunable rheological,tribological,electrochemical,infrared-emissive and photothermal-conversion properties based on the pH-induced changes in the surface chemistry of Ti_(3)C_(2)T_(x) nanosheets.By adopting a gel with optimized pH value,high lubrication,exceptional specific capacitances(~635 and~408 F g^(-1) at 5 and 100 mV s^(-1),respectively),long-term capacitance retention(~96.7%after 10,000 cycles)and high-precision screen-or extrusion-printing into different high-resolution anticounterfeiting patterns can be achieved,thus displaying extensive potential applications in the fields of semi-solid lubrication,control-lable devices,supercapacitors,information encryption and infrared camouflaging.

Preparation of polypyrrole-coated CuFe_2O_4 and their improved electrochemical performance as lithium-ion anodes

CuFe2O4 network,prepared via the electrostatic spray deposition technique,with high reversible capacity and long cycle lifetime for lithium ion battery anode material has been reported.The reversible capacity can be further enhanced by coating high electronic conductive polypyrrole（PPy）.At the current density of 100mA·g-1.Li/CuFe2O4 electrode delivers a reversible capacity of 842.9 mAh·g-1 while the reversible capacity of Li/PPy-coated CuFe2O4 electrode increases up to 1106.7 mAh-g’.A high capacity of 640.7 mAhg＂1 for the Li/PPy-coated CuFe2O4electrode is maintained in contrast of 398.9 mAh·g-1 for CuFe2O4 electrode after 60 cycles,which demonstrates good electrochemical performance of the composite due to the increase of electronic conductivity.The electrochemical impedance spectroscopy（EIS） further reveals that the Li/PPy-coated CuFe2O4 electrode has a lower charge transfer resistance than the Li/CuFe2C〉4 electrode.

Effects of Annealing Temperature on Microstructure and Sensing Properties to Alcohol for Nano-La_(0.68)Pb_(0.32)FeO_3

La_(0.68)Pb_(0.32)FeO_3 samples annealed at different temperature were prepared using citrate sol-gel method. With increasing of annealing temperature from 200 to 1000 ℃, the samples crystallize to have single-phase perovskite structure. However, the sensitivity increases at first due to the improvement of crystallization of the perovskite phase, and finally drops attributed to the larger grain size. The optimal sensitivities for La_(0.68)Pb_(0.32)FeO_3 samples annealed at 400, 600, 800, and 1000 ℃ are 12.14, 14.77, 51.07, and 34.55, respectively.

Adsorption removal of thiocyanate from aqueous solution by calcined hydrotalcite

A hydrotalcite with Mg/AI molar ratio 2 was prepared by co-precipitation method and was characterized by XRD, TG/DTA, Zeta potential and BET surface area. The hydrotalcite was calcined at 500℃, with the dehydration from interlayer, the dehydroxilation from the brucite-like layer and the decomposition of carbonate successively, transformed into the mixed oxide type. The removal of thiocyanate from aqueous solution by using the original hydrotalcite and calcined hydrotalcite （HTC-500） was investigated. The results showed that the thiocyanate adsorption capacity of calcined hydrotalcite was much higher than that of the original form. Calcined hydrotalcite was particularly effective at removing thiocyanate, and that the effective range of pH for the thiocyanate removal are between 5.5-10.0. The experimental data of thiocyanate removal fit nicely with Langmuir isotherm, and the saturated adsorption uptake was 96.2 mg SCN-/g HTC-500. The adsorption of thiocyanate by calcined hydrotalcite follows first-order kinetics. And the intercalation to the structure recovery for calcined hydrotalcite. But the presence of additional anions could affect the adsorption behavior of thiocyanate.

Efficient electrocatalytic reduction of carbon dioxide to ethylene on copper–antimony bimetallic alloy catalyst

The exploration of efficient electrocatalysts for the reduction of CO2 to C2H4 is of significant importance but is also a challenging subject.Cu-based bimetallic catalysts are extremely promising for efficient CO2 reduction.In this work,we synthesize a series of porous bimetallic Cu–Sb alloys with different compositions for the catalytic reduction of CO2 to C2H4.It is demonstrated that the alloy catalysts are much more efficient than the pure Cu catalyst.The performance of the alloy catalysts depended strongly on the composition.Further,the alloy with a Cu:Sb ratio of 10:1 yielded the best results;it exhibited a high C2H4 Faradaic efficiency of 49.7%and a high current density of 28.5 mA cm?2 at?1.19 V vs.a reversible hydrogen electrode(RHE)in 0.1 M KCl solution.To the best of our knowledge,the electrocatalytic reduction of CO2 to C2H4 using Cu–Sb alloys as catalysts has not been reported.The excellent performance of the porous alloy catalyst is attributed to its favorable electronic configuration,large surface area,high CO2 adsorption rate,and fast charge transfer rate.

Acidichromism in the LB film of bolaform Schiff base

A bolaform （BNC10） and single-headed （HNOA） amphiphilic Schiff bases containing naphthyl group were designed and their Langmuir-Blodgett films were investigated. It was found that both the LB films show acidichromism, i.e. a reversible color change upon alternatively exposing the films to HC1 and NH3 gases, respectively. It was further found that the bolaform Schiff bases film could trap NH3 gas during the acidichromic process.

Rheological properties of wormlike micelles formed in the sodium oleate/trisodium phosphate aqueous solution

Aqueous solution of anionic surfactant,sodium oleate（NaOA）,was studied by means of steady-state shear rheology and dynamic oscillatory technique.The system of NaOA/Na3PO4 showed high viscosity,strong viscoelasticity and good ability of countering Ca^2＋,Mg^2＋.The Maxwell model and Cole-Cole plot were applied to study the dynamic viscoelasticity of wormlike micelles.The microstructures of the wormlike micelles were characterized by FF-TEM.

Controllable oxygen vacancies and morphology engineering:Ultra-high HER/OER activity under base–acid conditions and outstanding antibacterial properties

Introducing vacancy defects and unique morphology is an effective strategy to improve the catalytic performance of transition metal compounds.However,precisely controlling the amount of vacancy defects remains challenging.Here,we propose a facile and efficient hydrothermal accompanying an annealing method to synthesize a series of Mn-doped CoO nanomaterials with controllable oxygen vacancies and unique morphology.The oxygen vacancies amount can be precisely controlled by adjusting the Mndoping content and is positively correlated with catalytic performance.It was found that the oxygen vacancies amount can reach up to 38.2%over the Mn-doped CoO nanomaterials,resulting in ultra-high hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalytic activity(HER:25.6 and 37 m V at 10 m A cm^(-2);OER:301 and 322 m V at 50 m A cm^(-2))under both basic and acidic conditions,while reaching 10 m A cm^(-2) for an ultra-low cell voltage of only 1.52 V,which exceeds that of Pt/C/RuO_(2) and all reported non-noble metal oxide catalysts.The DFT calculations reveal oxygen vacancies can optimize H*and HOO*intermediates adsorption free energy,thus improving the HER and OER performance.Interestingly,the Mn-doped CoO with rich oxygen vacancies exhibits excellent antibacterial properties in vitro of biomedicine.This work provides new ideas and methods for the rational design and precise control of vacancy defects in transition metal compounds and explores their potential application value in electrochemical water splitting and biomedical fields.

Formation of hierarchical Fe7Se8 nanorod bundles with enhanced sodium storage properties

Ordered hierarchical architectures are attractive candidates for electrochemical energy storage applications.Herein,a facile self-template strategy is applied to prepare Fe7Se8 architectures with a monolithic structure via a self-synthesized single precursor and subsequent calcination at high temperature.With the support of oleylamine,the precursor is structurally targeted to engineer the Fe7Se8 microstructure,featuring nanorod bundles arranged along the longitudinal direction.Because of their ordered hierarchical structure,the Fe7Se8 nanorod bundles deliver a high reversible capacity of 300 m Ah g^-1 at 0.5 A g^-1,along with exceptional rate capability up to 20 A g^-1 and long-term cycle life over 8000 cycles,which represents the highest stability of Fe7Se8 anodes for sodium-ion batteries reported to date.The feasibility of the present strategy to prepare metal selenide structures highlights its promising potential for the rational and effective engineering of electrode materials responsible for the electrochemical performance of energy storage systems.

Rational screening of metal coating on Zn anode for ultrahigh-cumulative-capacity aqueous zinc metal batteries

Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.

Rationally designed hollow carbon nanospheres decorated with S,P co-doped NiSe_(2) nanoparticles for high-performance potassium-ion and lithium-ion batteries

Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in secondary batteries.In this work,hollow carbon(HC) nanospheres embedded with S,P co-doped NiSe_(2)nanoparticles are fabricated by "drop and dry" and "dissolving and precipitation" processes to form Ni(OH)2nanocrystals followed by annealing with S and P dopants to form nanoparticles.The resultant S,P-NiSe_(2)/HC composite exhibits excellent cyclic performance with 131.6 mA h g^(-1)at1000 mA g^(-1)after 3000 cycles for K^(+)storage and a capacity of 417.1 mA h g^(-1)at 1000 mA g^(-1)after1000 cycles for Li^(+)storage.K-ion full cells are assembled and deliver superior cycling stability with a ca pacity of 72.5 mA h g^(-1)at 200 mA g^(-1)after 500 cycles.The hollow carbon shell with excellent electrical conductivity effectively promotes the transporta tion and tolerates large volume variation for both K^(+)and Li^(+).Density functional theory calculations confirm that the S and P co-doping NiSe_(2) enables stronger adsorption of K^(+)ions and higher electrical conductivity that contributes to the improved electrochemical performance.