Self-regulation in chemical and bio-engineering materials for intelligent systems

Herein, the authors review the self-regulation system secured by well-designed hybrid materials, composites, and complex system. As a broad concept, the self-regulated material/system has been defined in a wide research field and proven to be of great interest for use in a biomedical system, mechanical system, physical system, as the fact of something such as an organisation regulating itself without intervention from external perturbation. Here, they focus on the most recent discoveries of self-regulation phenomenon and progress in utilising the self-regulation design. This paper concludes by examining various practical applications of the remarkable materials and systems including manipulation of the oil/water interface, cell out-layer structure, radical activity, electron energy level, and mechanical structure of nanomaterials. From material science to bioengineering, self-regulation proves to be not only viable, but increasingly useful in many applications. As part of intelligent engineering, self-regulatory materials are expected to be more used as integrated intelligent components.

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

Synthesis and electrochemical properties of LiNi_(0.8)Al_(0.2-x)Ti_xO_2 cathode materials by an ultrasonic-assisted co-precipitation method

A new co-precipitation route was proposed to synthesize LiNi0.8A10.2-xTixO2 （x=0.0-0.20） cathode materials for lithium ion batteries, with Ni（NO3）2, Al（NO3）3, LiOH·H2O, and TiO2 as the starting materials. Ultrasonic vibration was used during preparing the precursors, and the precursors were protected by absolute ethanol before calcination in the air. The influences of doped-Ti content, calcination temperature and time, additional Li content, and ultrasonic vibration on the structure and properties of LiNi0.8A10.2-xTixO2 were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and charge-discharge tests, respectively. The results show that the optimal molar fraction of Ti, calcination temperature and time, and additional molar fraction of Li for LiNi0.8A10.2-xTixO2 cathode materials are 0.1,700℃, 20 h, and 0.05, respectively. Ti doping facilitates the formation of the α-NaFeO2 layered structure, and ultrasonic vibration improves the electrochemical performance of LiNi0.8A10.2-xTixO2.

Increasing both the electromagnetic shielding and thermal conductive properties of three-dimensional graphene-CNT-SiC hybrid materials

During the operation of electronic devices,a considerable amount of heat and electromagnetic radiation is emitted.Therefore,the investigation of materials with electromagnetic shielding and thermal management abilities has significant importance.Hybrid materials of three-dimensional graphene networks containing both carbon nanotubes(CNTs)and SiC whiskers(3D graphene-CNT-SiC)were synthesized.Using an aqueous-phase reduction method for the self-assembly of the graphene oxide,a three-dimen-sional porous graphene structure was fabricated.SiC whiskers,inserted between the graphene layers,formed a framework for longit-udinal thermal conduction,while CNTs attached to the SiC surface,created a dendritic structure that increased the bonding between the SiC whiskers and graphene,improving dielectric loss and thermal conductivity.It was found that the thermal conductivity of the hybrid material reached 123 W·m^(-1)·K^(-1),with a shielding effectiveness of 29.3 dB when the SiC addition was 2%.This result indic-ates that 3D graphene-CNT-SiC has excellent thermal conductivity and electromagnetic shielding performance.

Structure and electrochemical properties of La, F dual-doped LiLa_(0.01)Mn_(1.99)O_(3.99)F_(0.01) cathode materials

The cathode materials LiMn2O4 and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides.were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis （DTA） and thermogravimetry （TG） measurements, X-ray diffraction （XRD）, scanning electronic microscope （SEM）, cyclic voltammetry （CV）, and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa0.01Mn1.99O3.99F0.01 and LiLao.olMnl.9904 samples have smaller lattice parameters and unit cell volume than LiMn2O4. SEM indicates that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn2O4, LiLa0.01Mn1.99O4, and LiLa0.01Mn1.99O3.99F0.01 are 129.9, 122.8, and 126.4 mAh·g^-1, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn2O4.

Solution-based Chemical Strategies to Purposely Control the Microstructure of Functional Materials

Micro/nanostructured crystals with controlled architectures are desirable for many applications in optics, electronics, biology, medicine, and energy conversions. Low-temperature, aqueous chemical routes have been widely investigated for the synthesis of particles, and arrays of oriented nanorods and nanotubes. In this paper, based on the ideal crystal shapes predicted by the chemical bonding theory, we have developed some potential chemical strategies to tune the microstructure of functional materials, ZnS and Nb205 nanotube arrays, MgO wiskers and nestlike spheres, and cubic phase Cu2O microcrystals were synthesized here to elucidate these strategies. We describe their controlled crystallization processes and illustrate the detailed key factors controlling their growth by examining various reaction parameters. Current results demonstrate that our designed chemical strategies for tuning microstructure of functional materials are applicable to several technologically important materials, and therefore may be used as a versatile and effective route to the controllable synthesis of other inorganic functional materials.

Sandwiching Sulfur into the Dents Between N,O Co-Doped Graphene Layered Blocks with Strong Physicochemical Confinements for Stable and High-Rate Li-S Batteries

The development of lithium-sulfur batteries(LSBs)is restricted by their poor cycle stability and rate performance due to the low conductivity of sulfur and severe shuttle effect.Herein,an N,O co-doped graphene layered block(NOGB)with many dents on the graphene sheets is designed as effective sulfur host for high-performance LSB s.The sulfur platelets are physically confined into the dents and closely contacted with the graphene scaffold,ensuring structural stability and high conductivity.The highly doped N and O atoms can prevent the shuttle effect of sulfur species by strong chemical adsorption.Moreover,the micropores on the graphene sheets enable fast Li^+transport through the blocks.As a result,the obtained NOGB/S composite with 76 wt%sulfur content shows a high capacity of 1413 mAh g^-1 at 0.1 C,good rate performance of 433 mAh g^-1 at 10 C,and remarkable stability with 526 mAh g^-1 at after 1000 cycles at 1 C(average decay rate:0.038%per cycle).Our design provides a comprehensive route for simultaneously improving the conductivity,ion transport kinetics,and preventing the shuttle effect in LSBs.

Effects of chemical cues on larval survival,settlement and metamorphosis of abalone Haliotis asinina

Low larval survival,poor settlement,and abnormal metamorphosis are major problems in seed production of donkey-ear abalone Haliotis asinina.We examined the effects of chemical cues including epinephrine,nor-epinephrine,and serotonin on larval survival,settlement,and metamorphosis in order to determine the possibility of using these chemicals to induce the problems.The results show that epinephrine could enhance metamorphosis rate at 10-6 mol/L only but higher concentrations(10-3-10-4 mol/L);and nor-epinephrine could inhibit the performance significantly,and serotonin could increase significantly the performance at a wide-range concentration(10-3-10-6 mol/L).Treatment with serotonin at 10-5 mol/L for 72 hours resulted in the highest settlement rate(42.2%) and survival rate(49.3%),while at 10-4 mol/L for 72 hours resulted in the highest metamorphosis rate(38.8%).Therefore,serotonin may be used as a fast metamorphosis inducer in abalone culture.

Electrochemical behavior and underpotential deposition of Sm on reactive electrodes(Al,Ni,Cu and Zn)in a LiCl-KCl melt

Sm extraction from a LiCl-KCl melt was carried out by forming alloys on various electrodes,including Al,Ni,Cu,and liquid Zn,and the electrochemical behaviors of the resultant metal products were investigated using different electrochemical techniques.While Sm metal deposition via the conventional two-step reaction process was not noted on the inert electrode,underpotential deposition was observed on the reactive electrodes because of the latter's depolarization effect.The depolarization effects of the reactive electrodes on Sm showed the order Zn>Al>Ni>Cu.Sm-M(M=Al,Ni,Cu,Zn)alloys were deposited by galvanostatic and potentiostatic electrolysis.The products were fully characterized by X-ray diffractometry(XRD)and scanning electron microscopy(SEM)-energy dispersive spectrometry(EDS),and the stability of the obtained M-rich compounds was determined.Finally,the relationship between the electrode potential and type of Sm-M intermetallic compounds formed was assessed on the basis of the observed electrochemical properties and electrodeposits.

Chemical Bond Calculations of Crystal Growth of KDP and ADP

A novel method was proposed to calculate the crystal morphology (or growth habit) on the basis of chemical bond analysis. All constituent chemical bonds were distinguished as relevant and independent bonds according to their variations during the crystallization process. By employing the current method, the influence of specific growth conditions on the crystal morphology can be considered in the structure analysis process. The ideal morphologies of both KDP (KH2PO4) and ADP (NH4H2PO4) crystals were calculated and compared with our obtained crystallites at room temperature, which validates the present calculation method very well.

Distribution and Geochemical Implication of Aromatic Hydrocarbons across the Meishan Permian-Triassic Boundary

Aromatic compounds extracted from sedimentary rocks can reflect environmental conditions, organic sources and maturity. The aromatics, identified in association with mass extinction in particular, would provide a signature assisting our understanding of the causes of the biotic crisis. Aromatic hydrocarbons were fractionated from the total lipid extracts of 37 samples taken from the PermianTriassic boundary （beds 23 to 34） of section B at Meishan （煤山）, Zhejiang （浙江） Province in South China. These aromatics were analyzed by using gas chromatography-mass spectrometry （GC-MS）. Main compounds identified include naphthalene, phenanthrenes, fluorene, dibenzothiophene, dibenzofuran, fluoranthene, pyrene and some of their methyl homologues. The indices of methyl phenanthrene distribution fraction indicate the comparable maturity （within the oil window, 0.7%-1.0% of the mean vitfinite reflectance） of the organic matter throughout the whole profile analyzed. The ratio of dibenzothiophene to phenanthrene （DBT/PHN） varies generally at a comparable pace with lithology. Significantly, a gradual decrease of this ratio was observed within bed 24 limestone, which is probably due to the variation of sedimentary environment. This change is in line with the drop in the carbon isotope composition of carbonate, the loss of the Changhsingian reef ecosystem, and the decrease of cyanobacteria abundance within the bacteria population. The coincidence of these records suggests a close relation between the biotic crisis and marine environmental conditions, and these records clearly show the onset of the biotic crisis prior to event bed 25.

Instant formation of excellent oxygen evolution catalyst film via controlled spray pyrolysis for electrocatalytic and photoelectrochemical water splitting

The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge.However,there is a lack of facile techniques for depositing compact catalytic films of high coverage and possessing a state-of-the-art performance,which is especially desired in photoelectrochemical(PEC)systems.Herein,we demonstrate a spray pyrolysis(SP)route to address this issue,featuring the kinetic selective preparation towards the desired catalytic-active material.Differing from reported SP protocols which only produce inactive oxides,this approach directly generates a unique composite film consisting of NiFe layered oxyhydroxides and amorphous oxides,exhibiting an overpotential as small as 255 mV(10 mA cm^(−2))and a turnover frequency of∼0.4 s^(−1)per metal atom.By using such a facile protocol,the surface rate-limiting issue of BiVO_(4)photoanodes can be effectively resolved,resulting in a charge injection efficiency of over 90%.Considering this deposition directly start from simple nitrates but only takes several seconds to complete,we believe it can be developed as a widely applicable and welcomed functionalization technique for diverse electrochemical devices.

A Facile Synthesis of ZnCo2O4 Nanocluster Particles and the Performance as Anode Materials for Lithium Ion Batteries

ZnCo_2O_4 nanocluster particles(NCPs) were prepared through a designed hydrothermal method, with the assistance of a surfactant, sodium dodecyl benzene sulfonate. The crystalline structure and surface morphology of ZnCo_2O_4 were investigated by XRD, XPS, SEM, TEM, and BET analyses. The results of SEM and TEM suggest a clear nanocluster particle structure of cubic ZnCo_2O_4(*100 nm in diameter), which consists of aggregated primary nanoparticles(*10 nm in diameter), is achieved. The electrochemical behavior of synthesized ZnCo_2O_4 NCPs was investigated by galvanostatic discharge/charge measurements and cyclic voltammetry. The ZnCo_2O_4 NCPs exhibit a high reversible capacity of 700 mAh g^(-1) over 100 cycles under a current density of 100 mA g^(-1) with an excellent coulombic efficiency of 98.9% and a considerable cycling stability. This work demonstrates a facile technique designed to synthesize ZnCo_2O_4 NCPs which show great potential as anode materials for lithium ion batteries.

Nitrogen and Boron Co-Doped Carbon Nanotubes Embedded with Nickel Nanoparticles as Highly Efficient Electromagnetic Wave Absorbing Materials

Due to the limitations of impedance matching and attenuation matching,carbon nanotubes(CNTs)employed alone have a weak capacity to attenuate electromagnetic wave(EMW)energy.In this work,B and N co-doped CNTs with embedded Ni nanoparticles(Ni@BNCNTs)are fabricated via an in situ doping method.Compared with a sample without B doping,Ni@BNCNTs demonstrate a superior EMW absorption performance,with all minimum reflection loss values below−20 dB,even at a matching thickness of 1.5 mm.The experimental and theoretical calculation results demonstrate that B doping increases conduction and polarization relaxation losses,as well as the impedance matching characteristic,which is responsible for the enhanced EMW absorption performance of Ni@BNCNTs.

Deep Insight of Design,Mechanism,and Cancer Theranostic Strategy of Nanozymes

Since the discovery of enzyme-like activity of Fe3O4 nanoparticles in 2007,nanozymes are becoming the promising substitutes for natural enzymes due to their advantages of high catalytic activity,low cost,mild reaction conditions,good stability,and suitable for large-scale production.Recently,with the cross fusion of nanomedicine and nanocatalysis,nanozyme-based theranostic strategies attract great attention,since the enzymatic reactions can be triggered in the tumor microenvironment to achieve good curative effect with substrate specificity and low side effects.Thus,various nanozymes have been developed and used for tumor therapy.In this review,more than 270 research articles are discussed systematically to present progress in the past five years.First,the discovery and development of nanozymes are summarized.Second,classification and catalytic mechanism of nanozymes are discussed.Third,activity prediction and rational design of nanozymes are focused by highlighting the methods of density functional theory,machine learning,biomimetic and chemical design.Then,synergistic theranostic strategy of nanozymes are introduced.Finally,current challenges and future prospects of nanozymes used for tumor theranostic are outlined,including selectivity,biosafety,repeatability and stability,in-depth catalytic mechanism,predicting and evaluating activities.

Formation and transformation of metastable LPSO building blocks clusters in Mg-Gd-Y-Zn-Zr alloys by spinodal decomposition and heterogeneous nucleation

To study the formation and transformation mechanism of long-period stacked ordered(LPSO)structures,a systematic atomic scale analysis was conducted for the structural evolution of long-period stacked ordered(LPSO)structures in the Mg-Gd-Y-Zn-Zr alloy annealed at 300℃~500℃.Various types of metastable LPSO building block clusters were found to exist in alloy structures at different temperatures,which precipitate during the solidification and homogenization process.The stability of Zn/Y clusters is explained by the first principles of density functional theory.The LPSO structure is distinguished by the arrangement of its different Zn/Y enriched LPSO structural units,which comprises local fcc stacking sequences upon a tightly packed plane.The presence of solute atoms causes local lattice distortion,thereby enabling the rearrangement of Mg atoms in the different configurations in the local lattice,and local HCP-FCC transitions occur between Mg and Zn atoms occupying the nearest neighbor positions.This finding indicates that LPSO structures can generate necessary Schockley partial dislocations on specific slip surfaces,providing direct evidence of the transition from 18R to 14H.Growth of the LPSO,devoid of any defects and non-coherent interfaces,was observed separately from other precipitated phases.As a result,the precipitation sequence of LPSO in the solidification stage was as follows:Zn/Ycluster+Mg layers→various metastable LPSO building block clusters→18R/24R LPSO;whereas the precipitation sequence of LPSO during homogenization treatment was observed to be as follows:18R LPSO→various metastable LPSO building block clusters→14H LPSO.Of these,14H LPSO was found to be the most thermodynamically stable structure.

Effect of La Dopant on the Structure and Electrochemical Properties of LiCoO_2

The cathode material LiCo1-xLaxO2（x=0,0.01,0.02,0.05）for Li-ion battery was prepared in solid phase,Effects of La dopant on the structure were analyzed by X-ray diffraction.and the morphology of the samples was observed by scanning electron microscopy.The results show that the structure of LiCoO2 becomes more and more non-perfect with the4 increasing comtent of La and some impurity peaks appear in the XRD pattern when the La content reaches 0.05.Meamchile,a high synthesis temperature is advantageous to the intact and unitary compound,The initial discharge capacity of doped material containing La（x=0.01）synthesized at 900℃ reaches 160 mAh/g by charge-discharge test.which prior to that of non-doped material synthesized under the same condition.However,the increasing La content deteriorates the cycling performance.Therefore,the appropriate content of La is 0.01 and the optimum synthesis temperature is 900℃.

Investigation of Chemical Bond Properties and Mssbauer Spectroscopy in YBa_2Cu_3O_7

Chemical bond properties of YBa 2Cu 3O 7 were studied by using the average ba nd-gap model. The calculated results show that the covalency of Cu(1)-O bond i s 0.406, and one of Cu(2)-O is 0.276. Mssbauer isomer shifts of 57Fe in Y-123 were calculated by the chemical surrounding factor h v defined b y covalency and electronic polarizability. The charge-state and site of Fe were determined. The relation between the coupling constant of electron-phonon inte raction and covalency is employed to explain that the Cu(2)-O plane is more im portant than the Cu(1)-O chain on the superconductivity in the Y-123 compound s.

Synthesis and electrochemical properties of Th-doped LiMn_2O_4 powders for lithium-ion batteries

To improve the cycle performance of eco-friendly and cost-effective spinel LiMn2O4 as the Li secondary batteries, the Th-doped LiThxMn1-xO4 spinel powers were synthesized by solid-state method. The starting materials, Li2CO3, MnO2 and Th(NO3)4·4H2O, were mixed uniformly using a traditional ball milling, which resulted in a uniform particle size distribution in the mixed powers. Tests of X-ray diffraction, SEM, impedance spectra and charge-discharge were carried out for LiThxMn1-xO4 cathode materials. Results show that the synthesized LiTh0.01Mn1.99O4 material exhibits standard spinel structure, regular particle morphology and excellent property of charge-discharge for big current. The capacity retention of the material modified by doping Th is more than 85.1% of the first discharge specific capacity of 111.5 mAh·g-1 after 20 cycles at the current rate 1C, while the pristine LiMn2O4 is only 57% of the first discharge specific capacity of 110.2 mAh·g-1 after the same cycles at the same current rate.

Science Letters; In-situ synthesis and luminescence properties of titanium oxide gels containing 1,10-phenanthroline europium(Ⅲ) complex

It is difficult to directly dope europium complexes in gel because the excessive water or high acidic condition may lead to their decomposition. We prepared a novel homogeneous TiO2 gel containing Eu-phen complexes by using an in-situ synthesis method. The formation of Eu-phen complexes in sol-gel derived TiO2 was confirmed by luminescence excitation spectra. The effects of temperature and aging time on in-situ synthesis are discussed. The luminescence spectra of gel containing europium complexes were also compared with the pure Eu-phen complexes.