Interactions of Anionic and Neutral Serine with Pure and Metal-doped Graphene Studied by Density Functional Theory

We present a theoretical study of interactions of anionic and neutral serine （Ser） on pure or metal-doped graphene surfaces using density functional theory calculations. Interactions of both types of Ser with the pure graphene surface show weak non-covalent interactions due to the formation of-COOH…π, -COO^-…π, and -OH…π interactions. On metal- doped graphene, covalent interactions to the surface dominate, due to the formation of strong metal-O and O-metal-O interactions. Furthermore, the doped Fe, Cr, Mn, A1, or Ti enhances the ability of graphene to attract both types of Ser by a combination of the adsorption energy, the density of states, the Mulliken atomic charges, and differences of electron density. At the same time, the interaction strengths of anionic Ser on various graphene surfaces are stronger than those of neutral Ser. These results provide useful insights for the rational design and development of graphene-based sensors for the two forms of Ser by introducing appropriate doped atoms. Ti and Fe are suggested to be the best choices among all doped atoms for the anionic Ser and neutral Ser, respectively.

Metal-doped(Cu,Zn)Fe2O4 from integral utilization of toxic Zn-containing electric arc furnace dust: An environment-friendly heterogeneous Fenton-like catalyst

Pure metal-doped(Cu,Zn)Fe2O4 was synthesized from Zn-containing electric arc furnace dust(EAFD)by solid-state reaction using copper salt as additive.The effects of pretreated EAFD-to-Cu2(OH)2CO3·6H2O mass ratio,calcination time,and calcination temperature on the structure and catalytic ability were systematically studied.Under the optimum conditions,the decolorization efficiency and total organic carbon(TOC)removal efficiency of the as-prepared ferrite for treating a Rhodamine B solution were approximately 90.0%and 45.0%,respectively,and the decolorization efficiency remained 83.0%after five recycles,suggesting that the as-prepared(Cu,Zn)Fe2O4 was an efficient heterogeneous Fenton-like catalyst with high stability.The high catalytic activity mainly depended on the synergistic effect of iron and copper ions occupying octahedral positions.More importantly,the toxicity characteristic leaching procedure(TCLP)analysis illustrated that the toxic Zncontaining EAFD was transformed into harmless(Cu,Zn)Fe2O4 and that the concentrations of toxic ions in the degraded solution were all lower than the national emission standard(GB/31574-2015),further confirming that the as obtained sample is an environment-friendly heterogeneous Fenton-like catalyst.

Theoretical investigation of lithium ions’ nucleation performance on metal-doped Cu surfaces

Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as poor cycling performance,complicated interfacial reactions,low Coulombic efficiency,and uncontrollable lithium dendrites.Understanding Li^+ions’nucleation mechanism is essential to tackle the uncontrolled growth of lithium dendrites.However,the nucleation behavior of Li+ions is interfered by the structural complexities of existing substrates during the reduplicative plating/stripping process and the rational mechanism of uniform nucleation of Li^+ions has not been clearly understood from the theoretical point of view.In our work,first-principles theoretical calculations are carried out to investigate the Li^+ions nucleation performance on metal-doped Cu surfaces(MDCSs)and the key descriptors that determines the properties of various MDCSs are systematically summarized.It is found that the introduction of heterogeneous doping Ag and Zn atoms will induce a gradient adsorption energy on MDCSs,and such gradient deposition sites can reduce the diffusion barriers and accelerate the diffusion rates of Li+ions dynamically.By maneuvering the Li+ions nucleation on MDCSs,a dendrite-free lithium metal anode can be achieved without the use of porous matrixes and complex synthesis process,which can be attributed to suppress the uncontrollable lithium dendrites for realizing the high-efficiency LMBs.

Doped-TiO_2 Photocatalysts and Synthesis Methods to Prepare TiO_2 Films

TiO2 is a promising photocatalyst. However, the low photocatalytic efficiency calls for the modification of TiO2. Metal- and nonmetal-doping of TiO2 have been proved to be effective ways to enhance photocatalytic properties. This review provides a deep insight into the understanding of the metal- and nonmetal-doped TiO2 photocatalysts. This article begins with the introduction of the crystal structures of TiO2 and applications of TiO2 materials. We then reviewed the doped-TiO2 system in two categories： （1） metal-doped TiO2 photocatalysts system, and （2） nonmetal-doped TiO2 photocatalysts system. Both experimental results and theoretical analyses are elaborated in this section. In the following part, for the advantages of TiO2 thin films over particles, various preparation methods to obtain TiO2 thin films are briefly discussed. Finally, this review ends with a concise conclusion and outlook of new trends in the development of TiO2-based photocatalysts.

Structural and bonding properties of ScSi_n^-(n=2～6) clusters:photoelectron spectroscopy and density functional calculations

Anion ion photoelectron spectroscopy and density functional theory （DFT） are used to investigate the electronic and structural properties of ScSin （n = 2 - 6） clusters and their neutrals. We find that the structures of ScSin^- are similar to those of Sin＋1^-. The most stable isomers of ScSin^- cluster anions and their neutrals are similar for n=-2, 3 and 5 but different for n=4 and 6, indicating that the charge effect on geometry is size dependent for small scandiumsilicon clusters. The low electron binding energy （EBE） tails observed in the spectra of ScSi4,6^- can be explained by the existence of less stable isomers. A comparison between ScSin and VSin clusters shows the effects of metal size and electron configuration on cluster geometries.

Fabrication and magnetic properties of 4SC(NH_2)_2–Ni_(0.97)Cu_(0.03)Cl_2 single crystals

Single crystals of 4SC（NH2）2–Ni1-xCux Cl2（x = 0.03）（Cu-DTN） containing spin S = 1/2 Cu^2＋and S = 1 Ni^2＋cations are synthesized by slow evaporation methods. Structural characterization demonstrates that the Cu-DTN is of a tetrahedral structure with lattice parameter c being 9.0995 A, which is 1.32% expansion compared with that of parent material DTN due to the larger radius of the Cu ion. Direct current（DC） susceptibility measurements show that both the antiferromagnetic exchange interaction at low temperature and the large anisotropy of susceptibilities are suppressed after doping the Cu ion, which could be related to the structural distortion and the increase of the super-exchange paths in Cu-DTN.

Theoretical investigation of optical properties and band gap engineering for Zn1-xTMxTe(TM=Fe,Co)alloys by modified Becke-Johnson potential

The direct band gap ZnTe with transition metal （TM） impurities plays a vital role in optoelectronic and spintronic applications. In the present study, we use the advanced modified Becke-Johnson （mBJ） functional for performing the structural computations and detailed investigations of the optical characters in Zn1_xTMxTe （TM = Fe, Co） alloys with 0 ≤ x ≤1. By employing the FP-LAPW method, we determine various optical parameters for the ternary alloys and for the end binaries. The calculated static dielectric constants and optical band gaps for Zn1_xTMxTe （TM = Fe, Co） have an inverse relation that verifies the Penn model. We find that the static dielectric constant is nearly equal to the square of the static refractive index, and both increase with TM content. Furthermore, we also find a slight shift of peaks to a higher energy region with increasing TM concentration. The decreasing band gap and high value of the absorption in the visible region of electromagnetic spectrum make these alloys suitable for photonic and solar cell applications.

Tribological performance of various metal-doped carbon dots as water-based lubricant additives and their potential application as additives of poly(ethylene glycol)

Advances in nano-lubricant additives are vital to the pursuit of energy efficiency and sustainable development.Carbon dots(CDs)have been widely investigated in the domain of lubricant additives owing to their extraordinary tribological properties,in particular,their friction-reducing and anti-wear properties.Metal-doped CDs are a new type of CDs,and their friction-reducing and anti-wear properties are attracting increasing attention.Therefore,a series of CDs doped with various divalent metal ions have been successfully synthesized via one-pot pyrolysis.The tribological properties of the synthesized CDs as water-based lubricant additives are in the following order:Zn-CDs>Cu-CDs>>Mg-CDs>Fe-CDs>U-CDs.Specifically,adding 1.0 wt%of Zn-CDs into water-based lubricant results in 62.5%friction and 81.8%wear reduction.Meanwhile,the load-carrying capacity of the water-based lubricant increases from 120 N to at least 500 N.Zn-CDs as an additive have long service life.Additionally,anion-tuned Zn-CDs fabricated via anion exchange exhibit promise as lubricant additives for poly(ethylene glycol).Based on the results of wear scar surface analyses,it is discovered that tribochemical films,primarily composed of iron oxides,nitrides,metal carbonates,zinc oxides,zinc carbonates,organic compounds,and embedded carbon cores,formed on the rubbing surfaces with a thickness of approximately 270 nm when Zn-CDs are used as additives.This film combined with the“ball-bearing”and third-particle effects of Zn-CDs contributed to excellent lubrication performance.

Boosted microwave absorption performance of transition metal doped TiN fibers at elevated temperature

Due to the temperature and frequency response of electromagnetic(EM)loss,how to realize the effective design of microwave absorption materials(MWAMs)at elevated temperature is highly desirable for practical applications.Herein,transition metaldoped titanium nitride(M-TiN,M=Fe or Co)fibers were fabricated,the distortion of TiN lattice could cause the adjustable charge enrichment,which played a profound influence on the dielectric response and EM microwave absorption(EMWA)performances.Benefiting from the negative correlation between dielectric loss and temperature,more loss mechanism could be introduced,which would effectively enhance dielectric loss and EMWA performances at elevated temperature.The optimal EMWA performances of Fe-TiN fibers/polydimethylsiloxane(PDMS)composites were realized with a wide temperature range(298–423 K):the reflection loss(RL)could reach 99%(RL<−20 dB)at 12.2 GHz with 1.8 mm,when the filler content was only 15.0 wt.%.Compared with the undoped-TiN fibers/PDMS and Co-TiN fibers/PDMS composites,the excellent EMWA of Fe-TiN fibers/PDMS composite could be attributed to the reasonably synergistic polarization loss and conduction loss.Based on systematic analysis of the variable-temperature EM parameters and EMWA performances,the optimization of EMWA performances in wide temperature domain could be realized by introducing appropriate polarization loss and its compensating.Hopefully,this work provides a new strategy for regulating the dielectric response and designing effective MWAMs at elevated temperature.

One-Pot Three-Dimensional Printing Robust Self-Supporting MnO_(x)/Cu-SSZ-13 Zeolite Monolithic Catalysts for NH_(3)-SCR

Honeycomb cordierite coated with Cu-SSZ-13 zeolite is widely used for the selective catalytic reduction of NO_(x) with NH_(3)(NH_(3)-SCR)to reduce pollutants from vehicle emissions.However,conventional honeycomb catalysts fabricated via coating techniques are limited by low zeolite loadings,loss of the deposited zeolites,and complicated preparation processes.Herein,a facile,one-step three-dimensional(3D)printing strategy is developed to construct MnO_(x)/Cu-SSZ-13 monolithic catalysts with excellent catalytic performance for NH_(3)-SCR.Iron-containing halloysite nanotubes(Fe-HNTs)are introduced as printing ink additives to ensure mechanical stability and modulate the NH_(3)-SCR performance of monolithic catalysts in high temperature conditions.In situ incorporation of Mn into the Cu-SSZ-13 zeolite monoliths during the 3D printing process boosts the mechanical strength of the monolithic structures from 2.54 MPa to 4.33 MPa as well as broadens the temperature window(165-550℃)of the catalysts for NH_(3)-SCR with NO_(x) conversion of above 80%.Such robust multicomponent-integrated 3D-printed selfsupporting catalysts not only possess high zeolite loading and excellent catalytic activity,but also avoid complicated manufacturing processes,which contrasts with conventional honeycomb catalysts fabricated by extrusion coupled with coating.