Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution

Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

Facile Surface Engineering of NiCo_(2)O_(4) to Boost Propane Oxidation Activity

Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.

Preferentially selective extraction of lithium from spent LiCoO_(2)cathodes by medium-temperature carbon reduction roasting

Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.

A stepwise approach to enhancing flotation of low-grade zinnwaldite through the cationic/DL-2-octanol/anionic reagent combinations: Behavior and mechanism analysis

In order to alleviate the pressure on the supply of lithium resources, this research proposes the use of binary/ternary collectors with high selectivity and collecting ability to enhance the flotation purification of low-grade zinnwaldite ore. The binary collector is a mixture of dodecylamine polyoxyethylene ether and DL-2-octanol. A binary collector is added first, followed by sodium oleate, known as a ternary collector. Under acidic conditions, the recovery of Li2O in the concentrate was increased by 8.26% with the binary collector and 13.70% with the ternary collector, compared to the dodecylamine polyoxyethylene ether. The binary collector enhanced the dispersibility of the single collector, while co-adsorption strengthened the hydrophobic nature of the zinnwaldite surface. Consequently, zinnwaldite particles,after the application of binary collector, displayed inter-particle flocculation and attachment to bubbles within 60×10^(-9)m compared to other particles. Ternary collector exhibited the capacity to lower critical micelle concentration and surface tension, subsequently inducing a denser and thicker hydrophobic layer through electrostatic forces, hydrophobic interactions, and chemical reactions. The objective of this research is to facilitate the recovery of lithium resources from low-grade ores in order to meet the needs of sustainable development.

Revealing interfacial charge redistribution of homologous Ru-RuS_(2) heterostructure toward robust hydrogen oxidation reaction

Precisely tailoring the surface electronic structures of electrocatalysts for optimal hydrogen binding energy and hydroxide binding energy is vital to improve the sluggish kinetics of hydrogen oxidation reac-tion(HOR).Herein,we employ a partial desulfurization strategy to construct a homologous Ru-RuS_(2) heterostructure anchored on hollow mesoporous carbon nanospheres(Ru-RuS_(2)@C).The disparate work functions of the heterostructure contribute to the spontaneous formation of a unique built-in electric field,accelerating charge transfer and boosting conductivity of electrocatalyst.Consequently,Ru-RuS_(2)@C exhibits robust HOR electrocatalytic activity,achieving an exchange current density and mass activity as high as 3.56 mA cm^(-2) and 2.13 mAμg_(Ru)^(-1),respectively.exceeding those of state-of-the-art Pt/C and most contemporary Ru-based HOR electrocatalysts.Surprisingly,Ru-RuS_(2)@C can tolerate 1000 ppm of cO that lacks in Pt/C.Comprehensive analysis reveals that the directional electron transfer across Ru-RuS_(2) heterointerface induces local charge redistribution in interfacial region,which optimizes and balances the adsorption energies of H and OH species,as well as lowers the energy barrier for water formation,thereby promoting theHoR performance.

Crystallization of battery-grade lithium carbonate with high recovery rate via solid-liquid reaction

Lithium carbonate(Li_(2)CO_(3))stands as a pivotal raw material within the lithium-ion battery industry.Hereby,we propose a solid-liquid reaction crystallization method,employing powdered sodium carbonate instead of its solution,which minimizes the water introduction and markedly elevates one-step lithium recovery rate.Through kinetic calculations,the Li_(2)CO_(3)solid-liquid reaction crystallization process conforms by the Avrami equation rather than shrinking core model,which means the dissolution rate of Na_(2)CO_(3)is the most important factor affecting the reaction process.The effects of reaction conditions such as temperature and stirring speed on the Li_(2)CO_(3)precipitation behavior were evaluated.The results indicated that temperature is a most essential parameter than other reaction conditions or stirring speed.The exceptional 93%recovery of Li_(2)CO_(3)at 90℃with a remarkable purity of 99.5%was achieved by using 1.2 M ratio of Na_(2)CO_(3)/Li_(2)SO_(4).This method provides a new idea for the efficient preparation of battery-grade Li_(2)CO_(3).

Increased Oxygen Vacancies in CuO-ZnO Snowflake-like Composites Drive the Hydrogenation of CO_(2) to Methanol

Cu/ZnO is widely used in the hydrogenation of carbon dioxide (CO_(2)) to methanol (CH_(3)OH) to improve the lowconversion rate and selectivity generally observed. In this work, a series of In, Zr, Co, and Ni-doped CuO-ZnO catalysts wassynthesized via a hydrothermal method. By introducing a second metal element, the activity and dispersion of the activesites can be adjusted and the synergy between the metal and the carrier can be enhanced, forming an abundance of oxygenvacancies. Oxygen vacancies not only adsorb CO_(2) but also activate the intermediates in methanol synthesis, playing a keyrole in the entire reaction. Co3O4-CuO-ZnO had the best catalytic performance (a CO_(2) conversion rate of 9.17%;a CH_(3)OHselectivity of 92.77%). This study describes a typical strategy for multi-component doping to construct a catalyst with anabundance of oxygen vacancies, allowing more effective catalysis to synthesize CH_(3)OH from CO_(2).

Engineering W/O/W pickering emulsion for the enhanced antigen delivery and immune responses

Tumor immunotherapy,particularly cancer vaccines,holds promise for combating cancer by harnessing tailored immune responses against malignant cells.However,conventional approaches face challenges in efficiently delivering antigens for optimal immune activation.Emulsion adjuvants,like MF59,enhance cellular uptake but struggle to induce robust CD8^(+)T cell responses.Here,we introduce a novel strategy employing a water-in-oil-in-water(W/O/W)multiple Pickering emulsion(mPE)for antigen delivery.The mPE,utilizing biocompatible,pH-sensitive particles,encapsulates antigens within the inner water phase,ensuring enhanced intracellular processing and dictating the intracellular fate of antigens for improved cross-presentation.In vitro and in vivo studies demonstrated that mPEs induced robust dendritic cells activation and antigen cross-presentation,leading to a significantly enhanced immune response.Notably,calcium phosphate-stabilized mPE(CaP-mPE)illustrated the more robust IFN-γ^(+)T cell responses.In comparison with traditional surfactant-stabilized multiple emulsions,CaP-mPE significantly inhibit tumor growth and effectively prolong the survival of tumor-bearing mice.This innovative approach offers a promising avenue for the development of effective cancer vaccines with potent cellular immune responses.

The potential of ionic liquids in biopharmaceutical engineering

Biopharmaceuticals,such as proteins,peptides,nucleic acids and vaccines,bring about great hopes for the prevention and treatment of various diseases,but the industrialization of these products still faces challenges such as structural instability,inefficient bioactivity and low bioavailability.Ionic liquids(ILs),the marvelous solvent media with inimitable and tunable properties,may provide alternative solutions to overcome the above problems of biopharmaceutical industry.Progress has gradually been made through studies by combination of ILs with biomacromolecules.The applications involved the stabilization,protection,and delivery of biopharmaceuticals.Recent trends are being forwarded to using ILs in vaccines and nucleic acid drugs.However,challenges remain on the toxicity and safety issues.Besides,the cost of adding ILs to the benefits of biopharmaceuticals need to be considered.

Interfacial engineering of transition-metal sulfides heterostructures with built-in electric-field effects for enhanced oxygen evolution reaction

Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.

Anchoring nitrogen-doped Co_(2)P nanoflakes on NiCo_(2)O_(4)nanorod arrays over nickel foam as high-performance 3D electrode for alkaline hydrogen evolution

Effective and robust electrocatalysts are mainly based on innovative materials and unique structures.Herein,we designed a flakelike cobalt phosphide-based catalyst supporting on NiCo_(2)O_(4)nanorods array,which in-situ grew on the nickel foam(NF)current collector,referring as NCo_(2)P/NiCo_(2)O_(4)/NF electrode.By optimizing the microstructure and electronic structure through 3D hierarchy fabrication and nitrogen doping,the catalyst features with abundant electrochemical surface area,favorable surface wettability,excellent electron transport,as well as tailored d band center.Consequently,the as-prepared N-Co_(2)P/NiCo_(2)O_(4)/NF electrode exhibits an impressive HER activity with a low overpotentials of58 mV at 10 mA cm^(-2),a Tafel slop of 75 mV dec^(-1),as well as superior durability in alkaline medium.This work may provide a new pathway to effectively improve the hydrogen evolution performance of transition metal phosphides and to develop promising electrodes for practical electrocatalysis.

Identification and Pathogen Stimulation Patterns of Neuronal Nitric Oxide Synthase(nNOS)in Black Rockfish(Sebastes schlegelii)

Neuronal nitric oxide synthase(nNOS)was the producer of nitric oxide(NO)which played important gas messenger molecules in biological process.It also can take effect as immune regulation molecule in organism.Black rockfish(Sebastes schlegelii)is an important economic fish which were widely farmed in East Asia countries.Meanwhile,the pathogenic bacteria such as the Edwardsiella tarda and Vibrio anguillarum in seawater always brought serious obstacles to their healthy growth.In order to explore the expression pattern of n NOS gene under the pathogen stimulation and predict its immune function,the n NOS gene in black rockfish named Ssn NOS was identified.It was 3780 bp in length,located on chromosome 6,and contained 27 coding domain sequence(CDs).According to the phylogenetic analysis,the Ssn NOS showed closest relative to the counterpart gene of swamp eel(Monopterus albus).Meanwhile,analysis of Ssn NOS expression in various healthy tissues showed that Ssn NOS expression level was highest in healthy brain tissues,followed by intestinal tissues.In addition,Ssn NOS showed significant expression changes in response to stimulation by two pathogens.Particular in gill,the expression of Ssn NOS after pathogenic stimulation increased significantly.The Elisa analysis showed the Ssn NOS content in gills was much higher than that in other tissues at all time points.Moreover,the expression patterns of Ssn NOS in brain,intestine and kidney after stimulation by pathogens showed a distinct expression pattern which first down-regulated and then up-regulated.Therefore,the Ssn NOS may be an important signaling molecule for fish to respond rapidly in immune stimulation.

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.

Neuronal conversion from glia to replenish the lost neurons

Neuronal injury,aging,and cerebrovascular and neurodegenerative diseases such as cerebral infarction,Alzheimer’s disease,Parkinson’s disease,frontotemporal dementia,amyotrophic lateral sclerosis,and Huntington’s disease are characte rized by significant neuronal loss.Unfo rtunately,the neurons of most mammals including humans do not possess the ability to self-regenerate.Replenishment of lost neurons becomes an appealing therapeutic strategy to reve rse the disease phenotype.Transplantation of pluripotent neural stem cells can supplement the missing neurons in the brain,but it carries the risk of causing gene mutation,tumorigenesis,severe inflammation,and obstructive hydrocephalus induced by brain edema.Conversion of neural or non-neural lineage cells into functional neurons is a promising strategy for the diseases involving neuron loss,which may overcome the above-mentioned disadvantages of neural stem cell therapy.Thus far,many strategies to transfo rm astrocytes,fibroblasts,microglia,Muller glia,NG2 cells,and other glial cells to mature and functional neurons,or for the conversion between neuronal subtypes have been developed thro ugh the regulation of transcription factors,polypyrimidine tra ct binding protein 1(PTBP1),and small chemical molecules or are based on a combination of several factors and the location in the central nervous system.However,some recent papers did not obtain expected results,and discrepancies exist.Therefore,in this review,we discuss the history of neuronal transdifferentiation,summarize the strategies for neuronal replenishment and conversion from glia,especially astrocytes,and point out that biosafety,new strategies,and the accurate origin of the truly co nverted neurons in vivo should be focused upon in future studies.It also arises the attention of replenishing the lost neurons from glia by gene therapies such as up-regulation of some transc ription factors or downregulation of PTBP1 or drug interfe rence therapies.

Pickering emulsion transport in skeletal muscle tissue:A dissipative particle dynamics simulation approach

Lymph node targeting is a commonly used strategy for particulate vaccines,particularly for Pickering emulsions.However,extensive research on the internal delivery mechanisms of these emulsions,especially the complex intercellular interactions of deformable Pickering emulsions,has been surprisingly sparse.This gap in knowledge holds significant potential for enhancing vaccine efficacy.This study aims to address this by summarizing the process of lymph-node-targeting transport and introducing a dissipative particle dynamics simulation method to evaluate the dynamic processes within cell tissue.The transport of Pickering emulsions in skeletal muscle tissue is specifically investigated as a case study.Various factors impacting the transport process are explored,including local cellular tissue environmental factors and the properties of the Pickering emulsion itself.The simulation results primarily demonstrate that an increase in radial repulsive interaction between emulsion particles can decrease the transport efficiency.Additionally,larger intercellular gaps also diminish the transport efficiency of emulsion droplet particles due to the increased motion complexity within the intricate transport space compared to a single channel.This study sheds light on the nuanced interplay between engineered and biological systems influencing the transport dynamics of Pickering emulsions.Such insights hold valuable potential for optimizing transport processes in practical biomedical applications such as drug delivery.Importantly,the desired transport efficiency varies depending on the specific application.For instance,while a more rapid transport might be crucial for lymph-node-targeted drug delivery,certain applications requiring a slower release of active components could benefit from the reduced transport efficiency observed with increased particle repulsion or larger intercellular gaps.

Conjugated microporous polymers-scaffolded enzyme cascade systems with enhanced catalytic activity

Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2))is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2)interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO_2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction （XRD）. The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm^2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

Simultaneous extraction of gold and zinc from refractory carbonaceous gold ore by chlorination roasting process

A novel process based on chlorination roasting was proposed to simultaneously recover gold and zinc from refractory carbonaceous gold ore by using NaCl as chlorination agent.The effects of roasting temperature,roasting time and NaCl content on the volatilization rates of gold and zinc were investigated.The reaction mechanism and the phase transition process were also analyzed by means of SEM,EDS and XRD.The results demonstrated that under the optimal conditions of NaCl content of 10%,roasting temperature of 800℃,roasting time of 4 h and gas flow rate of 1 L/min,the rates of gold and zinc were 92%and 92.56%,respectively.During low-temperature chlorination roasting stage,a certain content of sulfur was beneficial to the chlorination reactions of gold and zinc;and during high-temperature chlorination roasting stage,the crystal structure of vanadium-bearing mica was destroyed,and the vanadium-containing oxides were beneficial to the chlorinating volatilization of gold and zinc.Eventually,the chlorinated volatiles of gold and zinc could be recovered by alkaline solution.

Recovery of valuable metals from a low-grade nickel ore using an ammonium sulfate roasting-leaching process

Metal leaching from a low-grade nickel ore was investigated using an ammonium sulfate roasting-water leaching process. The nickel ore was mixed with ammonium sulfate, followed by roasting and finally leaching with water. During the process the effects of the amotmt of ammonium sulfate, roasting temperature, and roasting time on the leaching recovery of metal elements were analyzed. The optimum technological parameters were determined as follows： ammonium sulfate/ore ratio, 0.8 g/g; roasting temperature, 400℃; and roasting time, 2 h. Under the optimum condition the leaching recoveries ofNi, Cu, Fe, and Mg were 83.48%, 76.24%, 56.43%, and 62.15%, respectively. Furthermore, the dissolution kinetics of Ni and Mg from the nickel ore was studied. The apparent activation energies for the leaching reaction of Ni and Mg were 18.782 and 10.038 kJ.mo1-1, which were consistent with the values of diffusion control reactions. Therefore, the results demonstrated that the leaching recoveries of Ni and Mg were controlled by diffusion.

Fluidized roasting reduction kinetics of low-grade pyrolusite coupling with pretreatment of stone coal

Based on the fluidized roasting reduction technology of low-grade pyrolusite coupling with pretreatment of stone coal, the manganese reduction efficiency was investigated and technical conditions were optimized. It is found that the optimum manganese reduction efficiency can be up to 98.97% under the conditions that the mass ratio of stone coal to pyrolusite is 3：1, the roasting temperature of stone coal is 1000℃, the roasting temperature of pyrolusite is 800℃, and the roasting time is 2 h. Other low-grade pyrolusite ores in China from Guangxi, Hunan, and Guizhou Provinces were tested and all these minerals responded well, giving -99% manganese reduction efficiency. Meanwhile, the reduction kinetic model has been established. It is confirmed that the reduction process is controlled by the interface chemical reaction. The apparent activation energy is 36.397 kJ/mol.