Super-exchange effect induced by early 3d metal doping on NiFe_(2)O_(4)(001)surface for oxygen evolution reaction

Understanding the intrinsic activity of oxygen evolution reaction(OER) is crucial for catalyst design.To date,different metal-doping strategies have been developed to achieve this,but the involving mechanisms remain unclear.Here,the electronic structure of the transition metal-doped NiFe_(2)O_(4)(001) surface is scrutinized for OER intrinsic activity using density functional theory calculations.Five 3d-orbital filling metals(Ti,V,Cr,Mn,and Co) are introduced as dopants onto A-and B-layers of the NiFe_(2)O_(4)(001) surface,and variation of oxidation states over Fe sites is observed on B-layer.Analyzing the magnetic moment and charge transfer of surface cation sites reveals that the variation of Fe oxidation states originates from the super-exchange effect and is influenced by the t2g-electron configuration of 3d metal dopants.This trend governs the generation of highly-active Fe3+sites on the B-layer,the adsorption strength of OER intermediates,i.e.,*O and*OH,and therefore the intrinsic activity.The finding of super-exchange mechanism induced by 3d early metal doping offers insights into electronic structure tailoring strategies for improving the intrinsic activity of OER electrocatalysts.

Long-distance super-exchange and quantum magnetic relaxation in a hybrid metal–organic framework

The hybrid metal-organic framework [（CH3）2NH2]Fe（HCOO）3 with a perovskite-like structure exhibits a variety of unusual magnetic behaviors at low temperatures. While the long-distance super-exchange through the Fe-（Y-CH-O- Fe exchange path leads to a canted antiferromagnetic ordering at TN - 19 K, a second transition of magnetic blocking develops at TB- 9 K. The stair-shaped magnetization hysteresis loops below TB resemble the behaviors of resonant quantum tunneling of magnetization in single-molecular quantum magnets. Moreover, the magnetic relaxation also exhibits several features of resonant quantum relaxation, such as the exponential law with a single characteristic relaxation time, and the nonmonotonic dependence of relaxation rate on the applied magnetic field with a much faster relaxation around the resonant fields. The origin of quantum tunneling behaviors in the [（CH3）2NH2]Fe（HCOO）3 metal-organic framework is discussed in terms of magnetic phase separation due to the modification of hydrogen bonding on the long-distance super-exchange interaction.

Toward High Performance Ambipolar Transport from Super-exchange Perspective:Theoretical Insights for IID-based Copolymers

High-performance ambipolar charge transport materials can reduce the manufacturing cost of OFET and OPV devices,and simplify circuit design and device structure.In order to obtain ambipolar donor-acceptor(D-A)polymer,many efforts have been made through different donor and acceptor combination,halogenation or heteroatom substitution.However,the influencing factor for charge transport polarity is still much complicated.Based on intra-chain super-exchange mechanism for D-A polymer,we found that the energy alignment of donor and acceptor moiety has large impact on charge transport polarity.When the HOMO-LUMO(H-L)gap of the acceptor moiety is narrow,its HOMO/LUMO energy level both lie between the HOMO and LUMO of the donor moiety(sandwich-type energy alignment),and the corresponding D-A copolymers will be more likely ambipolar transport.And thus,take a narrow H-L gap thiazoleisoindigo(TzIID)acceptor as an example,we demonstrated that a series of TzIID based copolymers combined with wide H-L gap donor moieties can reveal ambipolar transport.We further predict several high performance ambipolar D-A copolymers(TzIID-TT etc.)with balanced electron and hole transport,whose effective mass(m_(e)^(*)=0.146 and m_(h)^(*)=0.128)is one of the smallest effective masses among ambipolar materials.

Crystal Growth of Cu6(Ge,Si)6O18·6H2O and Assignment of UV-VIS Spectra in Comparison to Dehydrated Dioptase and Selected Cu(II) Oxo-Compounds Including Cuprates

Low-dimensional quantum spin systems with the Cu2+ central ion are still in the focus of experimental and theoretical research. Here is reported on growth of mm-sized single-crystals of the low-dimensional S = 1/2 spin compound Cu6(Ge,Si)6O18·6H2O by a diffusion technique in aqueous solution. A route to form Si-rich crystals down to possible dioptase, the pure silicate, is discussed. Motivated by previously reported incorrect assignments of UV-VIS spectra, the assignment of dd excitations from such spectra of the hexahydrate and the fully dehydrated compound is proposed in comparison to dioptase and selected Cu(II) oxo-compounds using bond strength considerations. Non-doped cuprates as layer compounds show higher excitation energies than the title compound. However, when the antiferromagnetic interaction energy as Jz·ln(2) is taken into account for cuprates, a single linear relationship between the Dqe excitation energy and equatorial Cu(II)-O bond strength is confirmed for all compounds. A linear representation is also confirmed between 2A1g energies and a function of axial and equatorial Cu-O bond distances if auxiliary axial bonds are used for four-coordinated compounds. The quotient Dt/Ds of experimental orbital energies deviating from the general trend to smaller values indicates the existence of H2O respectively Cl−axial ligands in comparison to oxo-ligands, whereas larger Dt/Dqe values indicate missing axial bonds. The quotient of the excitation energy 2A1g by 2·2Eg-2B2g allows checking for correctness of the assignment and to distinguish between axial oxo-ligands and others like H2O or Cl−.

Effect of rare earth(Nd^(3+))metal doping on structural,morphological,optical and magnetic traits of Zn-Mg nano-ferrites

Herein,we report the synthesis of Zn_(0.7)Mg_(0.3)Nd_(x)Fe_(2-x)O_(4)(where,x=0,0,0,01,0,02)ferrite nanoparticles by employing the sol-gel auto-combustion technique.The X-ray diffraction(XRD)pattern suggests the formation of a pure cubic structure,without any impurity phase,with an Fd3m space group at room temperature.With increasing doping amount,the crystallite size is reported as 35-41 nm,while the lattice parameters rise from 0.8381 to 0.8395 nm.Field emission scanning electron microscopy(FESEM)images show the formation of spherical grains with agglomerated morphology in all the samples,with grain sizes ranging from 49 to 103 nm.Energy dispersive X-ray spectroscopy(EDX)and elemental mapping investigation confirm the chemical purity of all the samples.Fourier transform infrared(FTIR)analysis shows the presence of two prominent peaks around 440 and 560 cm^(-1)that correspond to the octahedral and tetrahedral positions.In addition,the existence of five Raman active vibratio nal modes in all produced specimens again confirms the structural purity of all the samples.The M-H curve shows that saturation magnetization(M_(s))first increases from 14.98 to 28.22 emu/g and then decreases to 18.98emu/g with increasing doping amount.This is due to the A-B type super-exchange interaction for the synthesized samples.The variation in coercivity(H_(c))and magnetic anisotropy(K_(1))suggest the thermal stability of all the samples and can be utilized in transformers and solenoids.