Excess Activity Tuned by Distorted Tetrahedron in CoMoO_(4) for Oxygen Evolution

Oxygen vacancies enable modulating surface reconstruction of transition metal oxides containing metal-oxygen polyhedrons into metallic oxyhydroxide for oxygen evolution reaction(OER),while revealing reconstructing mechanism is stuck by the requirement to precisely control exact sites of these vacancies.Herein,oxygen vacancies are localized only within MoO_(4)tetrahedrons rather than CoO_(6)octahedrons in CoMoO_(4)catalyst,guaranteeing coherent reconstruction of CoO_(6)octahedrons into pure CoOOH with tunable activities for OER.Meanwhile,distorted tetrahedron accelerates the dissolution of Mo atoms into alkaline electrolyte,triggering spontaneous transition of partial CoMoO_(4)into Co(OH)_(2).CoO_(6)octahedrons in both CoMoO_(4)and Co(OH)_(2)can transform pure CoOOH completely at lower potential,resulting in excess intrinsic activity whose summit is identified by overpotential at 10 mA cm^(-2)with 22.9%reduction and Tafel slope with 65.3%reduction.Well-defined manipulation over the distorted polyhedrons offers one versatile knob to precisely modulate electronic structure of oxide catalysts with outstanding OER performance.

Chemical and boron isotopic compositions of tourmaline in the Longtoushan hydrothermal gold deposit, Guangxi, China:implications for gold mineralization

The Longtoushan hydrothermal gold deposit is located in the southwestern region of the Dayaoshan Uplift.Tourmaline is widespread in the Longtoushan gold deposit and is mainly distributed in the rhyolite porphyry and associated cryptoexplosive breccia. The spatial distribution of tourmaline enrichment is similar to that of the gold orebody. Feldspar has been largely replaced by tourmaline in the rhyolite porphyry and cryptoexplosive breccia.Electron microprobe analysis revealed that tourmalines in the Longtoushan deposit belong mainly to the alkali group and partly to the X-vacant group; they mostly fell in the schorl-dravite series field. Two distinct sets of dominant substitutions were observed: MgFe_(-1) and Al□(NaR2+)-1,where R = Fe, Mg. In addition, minor substitutions include(CaMg)(NaAl)_(-1) and FeAl_(-1). The calculated d11 B value for the mineralizing fluids ranged from-12.8 to-9.7%,which is typical of S-type granites, and boron-enriched fluids predominantly derived from rhyolitic melt. Part of the tourmaline from the rhyolite porphyry crystallized during the magmatic-hydrothermal stage, whereas most tourmalines from the deposit formed in the post-magmatic hydrothermal stage. The tourmalines were deposited from a relatively reduced and acidic fluid system, and the gold predominantly precipitated during the post-magmatic hydrothermal stage in the Longtoushan deposit.

Stabilization of heterogeneous hydrogenation catalysts for the aqueous-phase reactions of renewable feedstocks

The conversion of biomass-derived products to fine chemicals and fuels is extremely important for the utilization of renewable energy sources.Water is not only a by-product formed during the hydrogenation of biomass-derived oxygenated chemicals,but also an inexpensive and nontoxic solvent.The instability of solid catalysts for aqueous-phase reactions caused by metal leaching and the collapse of a catalyst support represents a significant challenge.In this work,various catalyst stabilization strategies including the nanospace and interfacial confinements that prevent sintering and leaching of metal nanoparticles as well as modification methods for increasing the support stability are summarized and systemically discussed.In addition,feasible approaches to designing stable and efficient heterogeneous catalysts for aqueous-phase reactions are proposed.

Aqueous-phase hydrogenation of levulinic acid over carbon layer protected silica-supported cobalt-ruthenium catalysts

The hydrogenation of levulinic acid(LA)to c-valerolactone(GVL)by using water as solvent is a crucial process in the production of fine chemicals from biomass.An ultrathin carbon layer coating CoRu bimetallic catalyst supported on silica(CoRu@C/SiO2)is prepared by using tannis-ligated cobalt-ruthenium complex on silica as precursors,and applied for catalyzed synthesis of GVL from LA.Because of the synergistic effect between cobalt and ruthenium,the addition of small amounts of Ru to Co catalysts can increase the catalytic activity in the aqueous hydrogenation of LA.The ultrathin carbon layer covered on the CoRu bimetallic catalyst can greatly reduce the leaching of active metals.The CoRu@C/SiO2 catalyst achieves high stability and is reused up to 5 runs without significant loss of performance in aqueous hydrogenation of levulinic acid.

Ammonium Metavanadate Fabricated by Selective Precipitation of Impurity Chemicals on Inorganic Flocculants

High purity ammonium metavanadate(NH_(4)VO_(3))is the most vital chemical to produce V2O5,VO2,VN alloy,VFe alloy and VOSO4,which have some prospective applications for high strength steel,smart window,infrared detector and imaging,large scale energy storage system.NH_(4)VO_(3)is usually produced by spontaneous crystallization from the aqueous solution due to its sharp dependence of solubility on the temperature.However,hazardous chemicals in industrial effluent,include phosphorate,silicate and arsenate,causing severe damage to the environment.In this work,these impurities are selectively precipitated onto inorganic flocculants,while the vanadate dissolved in an aqueous solution keeps almost undisturbed.Therefore,high purity NH_(4)VO_(3)is produced by the crystallization from the purified solution.By screening various flocculants and precipitating parameters,polyaluminum sulfate with an optimal amount of 50 g/L,is demonstrated to selectively remove phosphorate,silicate and arsenate,corresponding to the removing efficiency of 93.39%,97.11%and 88.31%,respectively.NH_(4)VO_(3)from the purified solution holds a purity of 99.21%,in comparison with 98.33%in the product from the crude solution.This purifying technology cannot only produce NH_(4)VO_(3)with high added value,but also reduce the environmental pollution of waste liquid.

Self-Supported Nanoporous Gold with Gradient Tin Oxide for Sustainable and Efficient Hydrogen Evolution in Neutral Media

Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supported nanoporous Au-SnO_(x)(NP Au-SnO_(x))catalyst with gradient tin oxide surface could significantly enhance HER activity in neutral buffer solution(0.2 M PBS).The NP Au-SnO_(x)catalyst exhibits a low onset overpotential of 38 mV and a small Tafel slope of 79 mV dec^(−1).The current density of 10 mA cm^(−2)is manifested at an overpotential as low as 148 mV,representing the comparable performance of Pt/C catalyst.This high catalytic activity can retain at least 10 hours without any detectable decay.The superior HER activity is proposed to originate from the gradient SnO_(x)structure and metal/oxide interfaces in nanoporous ligaments.Furthermore,the X-ray photoelectron spectroscopy reveals that the gradient oxide in the ligament is remarkably stable during long-term reaction.

Geochronology and Geochemistry of the Granites from the Longtoushan Hydrothermal Gold Deposit in the Dayaoshan Area,Guangxi:Implication for Petrogenesis and Mineralization

The gold mineralization in the Longtoushan hydrothermal gold deposit is concentrated within the contact zone of the granitic complex. Whole rock geochemistry and in-situ U-Pb and Hf isotopic data were used to constrain the genesis and age of the granites and related Cu-Au mineralization in the Longtoushan Deposit. The granites mainly consist of the granite porphyry, rhyolite porphyry, porphyritic granite and quartz porphyry. LA-ICP-MS U-Pb dating of zircons from the granite porphyry, rhyolite porphyry and quartz porphyry indicates that they intruded from ca. 94 to 97 Ma. These intrusions exhibit similar trace element characteristics, i.e., right-dipping REE patterns, depletion of Ba, Sr, P and Ti, and enrichment of Th, U, Nd, Zr and Hf. The εHf(t) values of zircons from the granite porphyry, rhyolite porphyry and quartz porphyry range from-26.81 to-8.19,-8.12 to-5.33, and-8.99 to-5.83, respectively, suggesting that they were mainly derived from the partial melting of the Proterozoic crust. The Cu-Au mineralization is mainly related to the rhyolite porphyry and porphyritic granite, respectively. The Longtoushan granites were most likely formed in a post-collisional extensional environment, and the deposit is a part of the Late Yanshanian magmatism related mineralization in the Dayaoshan area and its adjacent areas.

Nanoparticle monolayer-based flexible strain gauge with ultrafast dynamic response for acoustic vibration detection

The relatively poor dynamic response of current flexible strain gauges has prevented their wide adoption in portable electronics. In this work, we present a greatly improved flexible strain gauge, where one strip of Au nanoparticle （NP） monolayer assembled on a polyethylene terephthalate film is utilized as the active unit. The proposed flexible gauge is capable of responding to applied stimuli without detectable hysteresis via electron tunneling between adjacent nanoparticles within the Au NP monolayer. Based on experimental quantification of the time and frequency domain dependence of the electrical resistance of the proposed strain gauge, acoustic vibrations in the frequency range of 1 to 20,000 Hz could be reliably detected. In addition to being used to measure musical tone, audible speech, and creature vocalization, as demonstrated in this study, the ultrafast dynamic response of this flexible strain gauge can be used in a wide range of applications, including miniaturized vibratory sensors, safe entrance guard management systems, and ultrasensitive pressure sensors.

Convective Assembly of Linear Gold Nanoparticle Arrays at the Micron Scale for Surface Enhanced Raman Scattering

A convective assembly technique at the micron scale analogous to the writing action of a ＂pipette pen＂ has been developed for the linear assembly of gold nanoparticle strips with micron scale width and millimeter scale length for surface enhanced Raman scattering （SERS）. The arrays with interparticle gaps smaller than 3 nm are hexagonally stacked in the vicinity of the pipette tip. Variable numbers of stacked layers and clean surfaces of the assembled nanoparticles are obtained by optimizing the velocity of the pipette tip. The SERS properties of tile assembled nanoparticle arrays rely on their stacking number and surface cleanliness.

生物质基分子水相催化加氢反应及多相催化剂

生物质转化为平台分子,进一步转化成燃料和化学品是生物质利用的重要途径之一。本文总结了水相加氢反应及其催化剂的研究进展,指出了水相催化反应对催化剂的调控合成带来的挑战,如活性组分的流失,催化剂表面重构及毒化等。总结了水相催化加氢反应中高活性及高稳定性加氢催化剂的合成策略:如载体表面结构调控、炭的表面包覆、载体与金属活性组分之间相互作用的增强及新结构催化剂的设计合成等,指出了水相加氢反应的催化剂设计合成的发展方向,为生物质催化转化研究提供参考。

Controllable defects implantation in MoS2 grown by chemical vapor deposition for photoluminescence enhancement

Photoluminescence （PL） of transition metal dichalcogenides （TMDs） can be engineered by controlling the density of defects, which provide active sites for electron-hole recombination, either radiatively or non-radiatively. However, the implantation of defects by external stimulation, such as uniaxial tension and irradiation, tends to introduce local damages or structural non-homogeneity, which greatly degrades their luminescence properties and impede their applicability in constructing optoelectronic devices. In this paper, we present a strategy to introduce a controllable level of defects into the MoS2 monolayers by adding a hydrogen flow during the chemical vapor deposition, without sacrificing their luminescence characteristics. The density of the defect is controlled directly by the concentration of hydrogen. For an appropriate hydrogen flux, the monolayer MoS2 sheets have three times stronger PL emission at the excitonic transitions, compared with those samples with nearly perfect crystalline structure. The defect-bounded exciton transitions at lower energies arising in the defective samples and are maximized when the total PL is the strongest. However, the B exciton, exhibits a monotonic decline as the defect density increases. The Raman spectra of the defective MoS2 reveal a redshift （blueshift） of the in-plane （out-of-plane） vibration modes as the hydrogen flux increases. All the evidence indicates that the generated defects are in the form of sulfur vacancies. This study renders the high-throughput synthesis of defective MoS2 possible for catalysis or light emitting applications.

Closely packed nanoparticle monolayer as a strain gauge fabricated by convective assembly at a confined angle

The reliability and sensitivity of a strain gauge made from a nanoparticle monolayer intrinsically depend on electron tunneling between the adjacent nanoparticles, so that creating nanoscale interstitials with uniform distribution and tuning the interparticle separation reversibly during cyclic mechanical stress are two vital issues for performance enhancement. In this work, one assembly technique is initialized to fabricate parallel nanoparticle strips by precisely tailoring the contact angle of a gold colloid on a substrate. The assembly of a nanoparticle monolayer with a close-packed pattern can be simultaneously switched on and off by independently varying the contact angle across a threshold value of 4.2~. This nanoparticle strip shows a reversible and reliable electrical response even if a mechanical strain as small as 0.027% is periodically supplied, implying well-controlled electron tunneling between the adjacent nanoparticles.

Ultrasensitive strain gauge with tunable temperature coefficient of resistivity

We demonstrate an ultrasensitive strain gauge based on a discontinuous metal film with a record detection limit as low as 8.3 × 10^-6. Constructed by well-tunable crevices on the nanometer scale within the film, this gauge exhibits an ultrafast dynamic response to vibrations with a frequency range of 1 Hz to 10 kHz. More importantly, the temperature coefficient of resistivity （TCR） of the metal film is tunable owing to the cancellation effect caused by the possibility of tunneling across the nanoscale crevices （showing a negative temperature dependence） and the electron conduction within the metal islands （showing a positive temperature dependence）. Consequently, a nullified TCR is achievable when the crevice size can be precisely controlled. Thus, a fabrication strategy to precisely control the nanoscale crevices was developed in this study through the real-time tracking of the electrical conductivity during thermal evaporation. The ultrasensitive strain gauge with a tunable thermal drift introduces numerous opportunities for precision devices and wearable electronics with superior reliability.

Nanoporous Au-Sn with solute strain for simultaneously enhanced selectivity and durability during electrochemical CO2 reduction

Electrochemical carbon dioxide reduction meditated by metallic catalysts suffers from restricted selectivity and competition from hydrogen evolution, which sensitively depends on ambiguous contributions of alloying and strain state in bimetallic catalysts. Herein, nanoporous Au-Sn(NPAS) containing trace tin solute in Au lattices is delicately designed to convince real strain effect, while eliminating other undesirable factors, such as alloying, crystal facets and surface composition. Compared with nanoporous gold(NPG), the NPAS with a solute strain of ~2.2% enables more efficient CO2-to-CO conversion, with an efficiency as high as 92% at-0.85 V versus reversible hydrogen electrode(vs. RHE), and the high activity can retain for more than 8 h. The combination of HRTEM and surface valence band photoemission spectra reveals that the tensile strain on the surface of 3 D nanoporous structure promotes the catalytic activity by shifting up the d-band center and strengthening the adsorption of key intermediate *COOH. A small amount of Sn solute in the nanoporous alloy can prevent ligament coarsening effectively and improve the electrochemical stability.

Origin and the Hardening Mechanism of Twinned Lenticular Martensite in a Fe-33Ni Alloy

The twinned substructure of lenticular martensite in a quenched Fe–33Ni alloy was studied.In contrary to the traditional viewpoint that the twinned laths come from{112}<111>deformation twins and show insignificant hardening,we demonstrate that they are actually originated from the twinned Kurdjumov Sachs(KS)variants and can give rise to 3–4 times hardening up to~420 HV(~130 HV for the starting sample).The underlying mechanisms responsible for the propensity for twinned variants and the carbon-independent hardening for Fe–Ni system were discussed.

Advances in plant proteomics—key techniques of proteome

Following the completion of genome sequencing of model plants,such as rice(Oryza sativa L.)and Arabidopsis thaliana,the era of functional plant genomics has arrived which provides a solid basis for the develop-ment of plant proteomics.We review the background and concepts of proteomics,as well as the key techniques which include:(1)separation techniques such as 2-DE(two-dimensional electrophoresis),RP-HPLC(reverse phase high performance liquid chromatography)and SELDI(surface enhanced laser desorption/ionization)protein chip;(2)mass spectrometry such as MALDI-TOF-MS(matrix assisted laser desorption/ionization-time of flight-mass spectrometry)and ESI-MS/MS(electrospray ionization mass spectrometry/mass spectrometry);(3)Peptide sequence tags;(4)databases related to proteomics;(5)quantitative proteome;(6)TAP(tandem affinity purification)and(7)yeast two-hybrid system.In addition,the challenges and prospects of pro-teomics are also discussed.