Hydrothermal conversion of lignocellulosic biomass into high-value energy storage materials

Preparation of hierarchically porous, heteroatom-rich nanostructured carbons through green and scalable routes plays a key role for practical energy storage applications. In this work, naturally abundant lignocellulosic agricultural waste with high initial oxygen content, hazelnut shells, were hydrothermally carbonized and converted into nanostructured ‘hydrochar’. Environmentally benign ceramic/magnesium oxide（Mg O） templating was used to introduce porosity into the hydrochar. Electrochemical performance of the resulting material（HM700） was investigated in aqueous solutions of 1 M H;SO;, 6 M KOH and1 M Na;SO;, using a three-electrode cell. HM700 achieved a high specific capacitance of 323.2 F/g in 1 M H;SO;（at 1 A/g,-0.3 to 0.9 V vs. Ag/Ag Cl） due to the contributions of oxygen heteroatoms（13.5 wt%）to the total capacitance by pseudo-capacitive effect. Moreover, a maximum energy density of 11.1 Wh/kg and a maximum power density of 3686.2 W/kg were attained for the symmetric supercapacitor employing HM700 as electrode material（1 M Na;SO;, E = 2 V）, making the device promising for green supercapacitor applications.

Sulfur and nitrogen codoped cyanoethyl cellulose-derived carbon with superior gravimetric and volumetric capacity for potassium ion storage

We fabricated sulfur and nitrogen codoped cyanoethyl cellulose-derived carbons(SNCCs)with state-of-the-art electrochemical performance for potassium ion battery(PIB)and potassium ion capacitor(PIC)anodes.At 0.2,0.5,1,2,5,and 10 A g−1,the SNCC shows reversible capacities of 369,328,249,208,150,and 121 mA h g−1,respectively.Due to a high packing density of 1.01 g cm^(−3),the volumetric capacities are also uniquely favorable,being 373,331,251,210,151,and 122 mA h cm^(−3)at these currents,respectively.SNCC also shows promising initial Coulombic efficiency of 69.0%and extended cycling stability with 99.8%capacity retention after 1000 cycles.As proof of principle,an SNCC-based PIC is fabricated and tested,achieving 94.3Wh kg^(−1)at 237.5Wkg^(−1)and sustaining over 6000 cycles at 30 A g−1 with 84.5%retention.The internal structure of S and N codoped SNCC is based on highly dilated and defective graphene sheets arranged into nanometer-scale walls.Using a baseline S-free carbon for comparison(termed NCC),the role of S doping and the resultant dilated structure was elucidated.According to galvanostatic intermittent titration technique and electrochemical impedance spectroscopy analyses,as well as COMSOL simulations,this structure promotes rapid solid-state diffusion of potassium ions and a solid electrolyte interphase that is stable during cycling.X-ray diffraction was used to probe the ion storage mechanisms in SNCC,establishing the role of reversible potassium intercalation and the presence of KC36,KC24,and KC8 phases at low voltages.

Quantitative contributions of solution atoms, precipitates and deformation to microstructures and properties of Al-Sc-Zr alloys

In order to investigate the effects of solid solution atoms, precipitated particles and cold deformation on the microstructures and properties of Al-Sc-Zr alloys, the Al-Sc-Zr alloys prepared by continuous rheo-extrusion were treated by thermomechanical treatment, analyzed for conductivity and mechanical properties by tensile and microhardness testing, and characterized using optical microscope, TEM and STEM. A mathematical model was established to quantitatively characterize the contribution of solid solution atoms, precipitates and cold deformation to the conductivity of the alloy. The results show that the strength of Al alloy can be significantly improved by solid solution, aging and cold deformation, and the quantitative impacts of solution atoms, precipitates and cold deformation on the conductivity of Al alloy are 10.5%(IACS), 2.3%(IACS) and 0.5%(IACS), respectively. Aging and cold deformation treatments are the keys to obtain high-strength and high-conductivity aluminum alloy wires.

Effects of pre-precipitation of Cr_2N on microstructures and properties of high nitrogen stainless steel

Aging precipitation and solid solution heat treatment were carried out on three steels which have chromium content of 18%, manganese content of 12%, 15%, 18%, and nitrogen content of 0.43%, 0.53%, 0.67%, respectively. The mechanisms of precipitation and solid solution of high nitrogen anstenitic stainless steel were studied using the scanning electron microscopy, transmission electron microscopy, electron probe micro analysis and mechanical testing. The results show that, Cr2N is the primary precipitate in the tested stainless steels instead of Cr23C6. Cr2N nucleates at austenitic grain boundaries and grows towards inner grains with a lameUar morphology. By means of pre-precipitation of Cr2N at 800 ~C, the microstructure of the steels at solid solution state can be refined, thus improving the strength and plasticity. After the proposed treatment, the tensile strength, the proof strength and the elongation of the tested steel reach 881 MPa, 542 MPa and 54%, respectively.

Superhydrophobic fluoride conversion coating on bioresorbable magnesium alloy——fabrication,characterization,degradation and cytocompatibility with BMSCs

A micro-nano structure CaF_(2)chemical conversion layer was prepared on fluoride-treated AZ31 alloy,then the composite fluoride conversion film(CaF_(2)/MgF_(2))was modified by stearic acid(SA)and fabricated a superhydrophobic surface.The fluoride-treated magnesium,fluoride conversion film and superhydrophobic coating were characterized by SEM,EDS,XRD and FTIR.The properties of coatings1 adhesion and corrosion resistance were evaluated via tape test and electrochemical measurement.The cytocompatibility of the MgF_(2),CaF_(2)and superhydrophobic CaF_(2)/SA surface was investigated with bone marrow-derived mesenchymal stem cells(BMSCs)by direct culture for 24 h.The results showed that the superhydrophobic fluoride conversion coating composed of inner MgF_(2)layer and the outer CaF_(2)/SA composite layer had an average water contact angle of 152°.SA infiltrated into the micro-nano structure CaF_(2)layer and formed a strong adhesion with CaF_(2)layer.Furthermore,the super-hydrophobic coating showed higher barrier properties and corrosion resistance compared with the fluoride conversion film and fluoride-treated AZ31 alloy.The BMSC adhesion test results demonstrated MgF_(2)CaF_(2)and CaF_(2)/SA coatings were all nontoxic to BMSC.At the condition of in direct contact with cells,MgF_(2)showed higher cell density and enhanced the BMSCs proliferation,while CaF_(2)and CaF_(2)/SA coating showed no statistically difference in cell density compared with glass reference but the CaF_(2)and CaF_(2)/SA coating were not conducive to BMSCs adhesion.

Effect of retained austenite and nonmetallic inclusions on the thermal/electrical properties and resistance spot welding nuggets of Si-containing TRIP steels

Five advanced high-strength transformation-induced plasticity(TRIP) steels with different chemical compositions were studied to correlate the retained austenite and nonmetallic inclusion content with their physical properties and the characteristics of the resistance spot welding nuggets. Electrical and thermal properties and equilibrium phases of TRIP steels were predicted using the JMatPro? software. Retained austenite and nonmetallic inclusions were quantified by X-ray diffraction and saturation magnetization techniques. The nonmetallic inclusions were characterized by scanning electron microscopy. The results show that the contents of Si, C, Al, and Mn in TRIP steels increase both the retained austenite and the nonmetallic inclusion contents. We found that nonmetallic inclusions affect the thermal and electrical properties of the TRIP steels and that the differences between these properties tend to result in different cooling rates during the welding process. The results are discussed in terms of the electrical and thermal properties determined from the chemical composition and their impact on the resistance spot welding nuggets.

In vitro evaluation of degradation,cytocompatibility and antibacterial property of polycaprolactone/hydroxyapatite composite coating on bioresorbable magnesium alloy

Polycaprolactone/hydroxyapatite(PCL/HA)composite coating was fabricated by a combination of hydrothermal and dipping methods to delay the degradation of Mg alloy AZ31 as bioresorbable materials.The PCL/HA coating was composed of nano rod-shape HA crystals and PCL filled in the space of HA crystals.Compared with the single HA coating,the binding strength between the PCL/HA composite coating and Mg alloy was obviously improved and the PCL/HA coating still adhered to the surface of AZ31 substrate even after 38 days of immersion.The electrochemical corrosion rate of HA coated sample was reduced by ten times after being filled by PCL.The electrochemical impedance spectroscopy(EIS)and immersion test results showed that the PCL/HA composite coating could provide a more effective barrier for Mg substrate than the HA coating alone.The cytocompatibility and the antibacterial property of HA coating and PCL/HA coating were evaluated by culturing with bone marrow-derived mesenchymal stem cells(BMSCs)and methicillin-resistant staphylococcus aureus(MRSA)for 24 h under direct culture conditions,respectively.The PCL/HA composite coating showed better BMSC cell compatibility,more suitable for BMSC adhesion than HA coating alone and showed a potential application prospect as a biological materials.However,from the perspective of clinical applications,the antibacterial property of PCL/HA composite coating needs to be further improved.

Microstructure and Quasi-Static Mechanical Behavior of Cryoforged AA2519 Alloy

In this study, AA2519 alloy was initially processed by multi axial forging (MAF) at room and cryogenic temperatures. Subsequently, the microstructure and the mechanical behavior of the processed samples under quasi-static loading were investigated to determine the influence of cryogenic forging on alloys’ subgrains dimensions, grain boundaries interactions, strength, ductility and toughness. In addition, the failure mechanisms at the tensile rupture surfaces were characterized using scanning electron micro-scope (SEM). The results show significant improvements in the strength, ductility and toughness of the alloy as a result of the cryogenic MAF process. The formation of nanoscale crystallite microstructure, heavily deformed grains with high density of grain boundaries and second phase breakage to finer particles were characterized as the main reasons for the increase in the mechanical properties of the cryogenic forged samples. The cryogenic processing of the alloy resulted in the formation of an ultrafine grained material with tensile strength and toughness that are ~41% and ~80% higher respectively after 2 cycles MAF when compared with the materials processed at ambient temperature. The fractography analysis on the tested materials shows a substantial ductility improvement in the cryoforged (CF) samples when compared to the room temperature forged (RTF) samples which is in alignment with their stress-strain profiles. However, extended forging at higher cycles than 2 cycles led only to increase in strength at the expense of ductility for both the CF and RTF samples.

Multifunctional stimuli responsive polymer-gated iron and gold-embedded silica nano golf balls:Nanoshuttles for targeted on-demand theranostics

Multi-functional nanoshuttles for remotely targeted and on-demand delivery of therapeutic molecules and imaging to defined tissues and organs hold great potentials in personalized medicine, including precise early diagnosis, efficient prevention and therapy without toxicity. Yet, in spite of 25 years of research, there are still no such shuttles available. To this end, we have designed magnetic and gold nanoparticles （NP）-embedded silica nanoshuttles （MGNSs） with nanopores on their surface. Fluorescently labeled Doxombicin （DOX）, a cancer drug, was loaded in the MGNSs as a payload. DOX loaded MGNSs were encapsulated in heat and pH sensitive polymer P（NIPAM-co- MAA） to enable controlled release of the payload. Magnetically-guided transport of MGNSs was examined in： （a） a glass capillary tube to simulate their delivery via blood vessels; and （b） porous hydrogels to simulate their transport in composite human tissues, including bone, cartilage, tendon, muscles and blood-brain barrier {BBB）. The viscoelastic properties of hydrogels were examined by atomic force microscopy （AFM）. Cellular uptake of DOX- loaded MGNSs and the subsequent pH and temperature-mediated release were demonstrated in differentiated human neurons derived from induced pluripotent stem cells （iPSCs） as well as epithelial HeLa cells. The presence of embedded iron and gold NPs in silica shells and polymer-coating are supported by SEM and TEM. Fluorescence spectroscopy and microscopy documented DOX loading in the MGNSs. Time-dependent transport of MGNSs guided by an external magnetic field was observed in both glass capillary tubes and in the porous hydrogel. AFM results affirmed that the stiffness of the hydrogels model the rigidity range from soft tissues to bone. pH and temperature-dependent drug release analysis showed stimuli responsive and gradual drug release. Cells＇ viability MTT assays showed that MGNSs are non-toxic. The cell death from on-demand DOX release was observed in both neurons and epithelial cells even though the drug release efficiency was higher in neurons. Therefore, development of smart nanoshuttles have significant translational potential for controlled delivery of theranostics＇ payloads and precisely guided transport in specified tissues and organs （for example, bone, cartilage, tendon, bone marrow, heart, lung, liver, kidney, and brain） for highly efficient personalized medicine applications.

Quantifying Electrochemical Processes in Batteries and Beyond

The correlation of electrochemical measurements with materials characterization has advanced our understanding of operation and degradation mechanisms in electrochemical energy storage and many other fields.Yet,often these correlations are qualitative,preventing the unambiguous identification of both operational principles and the root causes of performance losses.Here we suggest quantitative approaches to define competing mechanisms and determine their relative contributions.We illustrate the importance of quantitative methodologies over a range of electrochemical systems and highlight the need to consider the effect of the experimental design and measurement itself.These approaches will reveal the most detrimental degradation mechanisms and enable the development of strategies to suppress,stabilize or eliminate them,leading to materials and devices with longer lifetimes,reduced environmental impact,and improved performance.

High pressure synthesis and characterization of the pyrochlore Dy2Pt2O7:A new spin ice material

The cubic pyrochlore Dy2Pt2O7 was synthesized under 4 GPa and 1000℃ and its magnetic and thermodynamic properties were characterized by DC and AC magnetic susceptibility and specific heat down to 0.1 K.We found that Dy2Pt2O7 does not form long-range magnetic order,but displays characteristics of canonical spin ice such as Dy2Pt2O7,including(1)a large effective moment 9.64μB close to the theoretical value and a small positive Curie-Weiss temperatureθCW=+0.77 K signaling a dominant ferromagnetic interaction among the Ising spins;(2)a saturation moment ~4.5μB being half of the total moment due to the local<111>Ising anisotropy;(3)thermally activated spin relaxation behaviors in the low(~1 K)and high(~20 K)temperature regions with different energy barriers and characteristic relaxation time;and most importantly,(4)the presence of a residual entropy close to Pauling’s estimation for water ice.

Facile, Green Synthesis of Large Single Crystal Copper Micro and Nanoparticles with Ascorbic Acid and Gum Arabic

Large single crystal colloidal copper particles with diameters between 0.5 - 2 μm were created using a green synthesis process. The process used ascorbic acid to reduce Schweizer’s reagent created in situ using copper salts in the presence of various concentrations of gum arabic. The Schweizer’s reagents were created by varying the concentrations of ammonium hydroxide and copper nitrate solutions, copper hydroxide, or copper sulfate. The pH of the solution was controlled by the addition of ascorbic acid. Particle formation was favored at high temperature using copper sulfate at pH values ranging from 7.5 to 9, while the optimal formation occurred at a pH value of 8.5. At high concentrations, copper particle formation was found to occur from the aggregation of smaller particles which continued to nucleate once aggregated, and this resulted in the creation of globular particles and large aggregates of micron-sized particles. The addition of gum arabic resulted in the creation of large single crystal particles that did not aggregate. SEM was used to observe the effect of increasing gum arabic concentrations and EDX was used to confirm the elemental purity of the particles.

Optimized CeO_(2) Nanowires with Rich Surface Oxygen Vacancies Enable Fast Li-Ion Conduction in Composite Polymer Electrolytes

Low-cost and flexible solid polymer electrolytes are promising in all-solid-state Li-metal batteries with high energy density and safety.However,both the low room-temperature ionic conductivities and the small Li^(+)transference number of these electrolytes significantly increase the internal resistance and overpotential of the battery.Here,we introduce Gd-doped CeO_(2) nanowires with large surface area and rich surface oxygen vacancies to the polymer electrolyte to increase the interaction between Gd-doped CeO_(2) nanowires and polymer electrolytes,which promotes the Li-salt dissociation and increases the concentration of mobile Li ions in the composite polymer electrolytes.The optimized composite polymer electrolyte has a high Li-ion conductivity of 5×10^(-4)4 S cm^(-1) at 30℃ and a large Li+transference number of 0.47.Moreover,the composite polymer electrolytes have excellent compatibility with the metallic lithium anode and high-voltage LiNi_(0.8)Mn _(0.1)Co_(0.1)O_(2)(NMC)cathode,providing the stable cycling of all-solid-state batteries at high current densities.

Entropy-modulated and interlayer-doped transition metal layered oxides enable high-energy-density sodium-ion capacitors

In recent years,sodium-ion capacitors have attracted attention due to their cost-effectiveness,high power density and similar manufacturing process to lithium-ion capacitors.However,the utilization of oxide electrodes in traditional sodium-ion capacitors restricts their further advancement due to the inherent low operating voltage and electrolyte consumption based on their energy storage mechanism.To address these challenges,we incorporated Zn,Cu,Ti,and other elements into Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2) to synthesize P2-type Na_(0.7)Ni_(0.28)Mn_(0.6)Zn_(0.05)Cu_(0.02)Ti_(0.05)O_(2) with a modulated entropy and pillaring Zn.Through the synergistic interplay between the interlayer pillar and the entropy modulation within the layers,the material exhibits exceptional toughness,effectively shielding it from detrimental phase transitions at elevated voltage regimes.As a result,the material showcases outstanding kinetic properties and long-term cycling stability across the voltage range.By integrating these materials with hierarchical porous carbon nanospheres to form a"rocking chair"sodium-ion capacitor,the hybrid full device delivers a high energy density(171 Wh·kg^(-1))and high power density(5245 W·kg^(-1)),as well as outstanding cycling stability(77% capacity retention after 3000 cycles).This work provides an effective material development route to realize simultaneously high energy and power for next-generation sodium-ion capacitors.

Fluorinated amphiphilic Poly(β-Amino ester)nanoparticle for highly efficient and specific delivery of nucleic acids to the Lung capillary endothelium

Endothelial cell dysfunction occurs in a variety of acute and chronic pulmonary diseases including pulmonary hypertension,viral and bacterial pneumonia,bronchopulmonary dysplasia,and congenital lung diseases such as alveolar capillary dysplasia with misalignment of pulmonary veins(ACDMPV).To correct endothelial dysfunction,there is a critical need for the development of nanoparticle systems that can deliver drugs and nucleic acids to endothelial cells with high efficiency and precision.While several nanoparticle delivery systems targeting endothelial cells have been recently developed,none of them are specific to lung endothelial cells without targeting other organs in the body.In the present study,we successfully solved this problem by developing non-toxic poly(β-amino)ester(PBAE)nanoparticles with specific structure design and fluorinated modification for high efficiency and specific delivery of nucleic acids to the pulmonary endothelial cells.After intravenous administration,the PBAE nanoparticles were capable of delivering non-integrating DNA plasmids to lung microvascular endothelial cells but not to other lung cell types.IVIS whole body imaging and flow cytometry demonstrated that DNA plasmid were functional in the lung endothelial cells but not in endothelial cells of other organs.Fluorination of PBAE was required for lung endothelial cell-specific targeting.Hematologic analysis and liver and kidney metabolic panels demonstrated the lack of toxicity in experimental mice.Thus,fluorinated PBAE nanoparticles can be an ideal vehicle for gene therapy targeting lung microvascular endothelium in pulmonary vascular disorders.

Morphology-controlled synthesis of multi-metal-based spinel oxide nanocatalysts and their performance for oxygen reduction

We present a one-pot colloidal synthesis method for producing monodisperse multi-metal(Co,Mn,and Fe)spinel nanocrystals(NCs),including nanocubes,nano-octahedra,and concave nanocubes.This study explores the mechanism of morphology control,showcasing the pivotal roles of metal precursors and capping ligands in determining the exposed crystal planes on the NC surface.The cubic spinel NCs,terminated with exclusive{100}-facets,demonstrate superior electrocatalytic activity for the oxygen reduction reaction(ORR)in alkaline media compared to their octahedral and concave cubic counterparts.Specifically,at 0.85 V,(CoMn)Fe_(2)O_(4) spinel oxide nanocubes achieve a high mass activity of 23.9 A/g and exhibit excellent stability,highlighting the promising ORR performance associated with{100}-facets of multi-metal spinel oxides over other low-index and high-index facets.Motivated by exploring the correlation between ORR performance and surface atom arrangement(active sites),surface element composition,as well as other factors,this study introduces a prospective approach for shapecontrolled synthesis of advanced spinel oxide NCs.It underscores the significance of catalyst shape control and suggests potential applications as nonprecious metal ORR electrocatalysts.

Phase separation and domain crystallinity control enable open-air-printable highly efficient and sustainable organic photovoltaics

Organic solar cells(OSCs)have emerged as a promising solution for sustainable energy production,offering advantages such as a low carbon footprint,short energy payback period,and compatibility with eco-solvents.However,the use of hazardous solvents continues to dominate the best-performing OSCs,mainly because of the challenges of controlling phase separation and domain crystallinity in eco-solvents.In this study,we combined the solvent vapor treatment of CS2 and thermal annealing to precisely control the phase separation and domain crystallinity in PM6:M-Cl and PM6:O-Cl systems processed with the eco-solvent o-xylene.This method resulted in a maximum power conversion efficiency(PCE)of 18.4%,which is among the highest values reported for sustainable binary OSCs.Furthermore,the fabrication techniques were transferred from spin coating in a nitrogen environment to blade printing in ambient air,retaining a PCE of 16.0%,showing its potential for high-throughput and scalable production.In addition,a comparative analysis of OSCs processed with hazardous and green solvents was conducted to reveal the differences in phase aggregation.This work not only underscores the significance of sustainability in OSCs but also lays the groundwork for unlocking the full potential of open-air-printable sustainable OSCs for commercialization.

Electrochemical corrosion behavior of bulk ultra-fine grained Fe-Ni-Cr alloy

The corrosion behavior of bulk ultra-fine grained（UFG） Fe-Ni-Cr alloy prepared by equal-channel angular pressing technique was investigated in 0.25 mol/L Na2SO4＋0.05 mol/L H2SO4 solution by electrochemical measurements.As compared to the coarse grained（CG） counterpart,the UFG alloy exhibits an acceleration of the active dissolution and a shrunk passive region with a higher passive current.The Mott-Schottky analysis in conjunction with the point defect model indicates mat the donor diffusion coefficient in the passive films of the UFG sample increases greatly to one magnitude order higher and the donor density is slightly lower than that of the CG sample.

Three-dimensional bioprinting of gelatin methacryloyl (GelMA)

The three-dimensional (3D)bioprinting technology has progressed tremendously over the past decade.By controlling the size, shape,and architecture of the bioprinted constructs,3D bioprinting allows for the fabrication of tissue/organ-like constructs with strong structural-functional similarity with their in vivo counterparts at high fidelity.The bioink,a blend of biomaterials and living cells possessing both high biocompatibility and printability,is a critical component of bioprinting.In particular, gelatin methacryloyl (GelMA)has shown its potential as a viable bioink material due to its suitable biocompatibility and readily tunable physicochemical properties.Current GelMA-based bioinks and relevant bioprinting strategies for GelMA bioprinting are briefly reviewed.

Bi_2Se_3/C Nanocomposite as a New Sodium-Ion Battery Anode Material

Bi_2Se_3 was studied as a novel sodium-ion battery anode material because of its high theoretical capacity and high intrinsic conductivity. Integrated with carbon,Bi_2Se_3/C composite shows excellent cyclic performance and rate capability. For instance, the Bi_2Se_3/C anode delivers an initial capacity of 527 mAh g^(-10) at 0.1 A g^(-1) and maintains 89% of this capacity over 100 cycles. The phase change and sodium storage mechanism are also carefully investigated.