Waste to wealth: Oxygen-nitrogen-sulfur codoped lignin-derived carbon microspheres from hazardous black liquors for high-performance DSSCs

Carbon materials are effective substitutes for Pt counter electrodes(CEs) in dye-sensitized solar cells(DSSCs). However, many of these materials, such as carbon nanotubes and graphene, are expensive and require complex preparation process. Herein, waste lignin, recycled from hazardous black liquors,is used to create oxygen-nitrogen-sulfur codoped carbon microspheres for use in DSSC CEs through the facile process of low-temperature preoxidation and high-temperature self-activation. The large number of ester bonds formed by preoxidation increase the degree of cross-linking of the lignin chains, leading to the formation of highly disordered carbon with ample defect sites during pyrolysis. The presence of organic O/N/S components in the waste lignin results in high O/N/S doping of the pyrolysed carbon,which increases the electrolyte ion adsorption and accelerates the electron transfer at the CE/electrolyte interface, as confirmed by density functional theory(DFT) calculations. The presence of inorganic impurities enables the construction of a hierarchical micropore-rich carbon structure through the etching effect during self-activation, which can provide abundant catalytically active sites for the reversible adsorption/desorption of electrolyte ions. Under these synergistic effects, the DSSCs that use this novel carbon CE achieve a quite high power-conversion efficiency of 9.22%. To the best of our knowledge, the value is a new record reported so far for biomass-carbon-based DSSCs.

Ga-N共同掺杂CoP催化氨硼烷制氢机理的理论研究

本文通过密度泛函理论(DFT),计算研究了金属原子Ga和非金属原子N共同掺杂磷化钴(CoP)作为催化剂催化氨硼烷(NH_(3) BH_(3))的脱氢过程.在这里,我们设计了四条可行的反应路径,并且计算了每条路径中间体过渡态的能量.通过研究结果得出结论,路径Ⅱ为最优反应路径.这将为金属和非金属共同掺杂CoP催化NH_(3) BH_(3)脱氢反应提供一定的理论基础.

Local coordination and electronic interactions of Pd/MXene via dual‐atom codoping with superior durability for efficient electrocatalytic ethanol oxidation

Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2)lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2)exhibits superior durability to its counterpart(∼14.6%retention)with 91.1%retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2)is capable of dehydrogenating ethanol at low reaction energies.

Charge-balanced codoping enables exceeding doping limit and ultralow thermal conductivity

Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities.However,the amount of equivalent heavyatom single dopant available is limited.Unfortunately,nonequivalent heavy dopants have finite solubility because of charge imbalance.Here,we propose a charge balance strategy for SnS by substituting Sn2+with Ag^(+)and heavy Bi^(3+),improving the doping limit of Ag from 2%to 3%.Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously,scattering the phonons at both the atomic scale and nanoscale.The thermal conductivity of Ag0.03Bi0.03Sn0.94S decreased to 0.535 W·m^(−1)·K^(−1)at room temperature and 0.388 W·m^(−1)·K^(−1)at 275°C,which is below the amorphous limit of 0.450 W·m^(−1)·K^(−1)for SnS.This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.

First-principles study of the electronic and optical properties of the (Y,N)-codoped anatase TiO_2 photocatalyst

First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. The calculated results show that Y and N codoping leads to lattice distortion, easier separation of photogenerated electron-hole pairs and band gap narrowing. The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping, which enhances visible-light photocatalytic activity.

Impact of Oxygen Vacancy on Band Structure Engineering of n-p Codoped Anatase TiO2

Doping with various impurities is an effective approach to improve the photoelectrochemical properties of TiO2. Here, we explore the effect of oxygen vacancy on geometric and elec- tronic properties of compensated （i.e. V-N and Cr-C） and non-compensated （i.e. V-C and Cr-N） codoped anatase TiO2 by performing extensive density functional theory calculations. Theoretical results show that oxygen vacancy prefers to the neighboring site of metal dopant （i.e. V or Cr atom）. After introduction of oxygen vacancy, the unoccupied impurity bands located within band gap of these codoped TiO2 will be filled with electrons, and the posi- tion of conduction band offset does not change obviously, which result in the reduction of photoinduced carrier recombination and the good performance for hydrogen production via water splitting. Moreover, we find that oxygen vacancy is easily introduced in V-N codoped TiO2 under O-poor condition. These theoretical insights are helpful for designing codoped TiO2 with high photoelectrochemical performance.

Electrochemical performance of C-La^(3+) codoped LiFePO_4 synthesized by microwave heating

La3+ was selected to elevate the lattice electronic conductivity of LiFePO4,and LiFePO4/(C+La3+) cathode powders were synthesized by microwave heating using a domestic microwave oven for 35 min. The microstructures and morphologies of the synthesized materials were investigated by XRD and SEM. The electrochemical performances were evaluated by galvanostatic charge-discharge. The electrochemical performance of LiFePO4 with different La3+ contents was studied. Results indicated that the initial specific disch...

First-principles calculation of electronic properties of N-and X(X=S,Se,Te)-codoped anatase TiO_2

The impact of N-and X（X=S,Se,Te）-codoping on electronic properties of anatase TiO2 has been systematically investigated using density functional theory （DFT）.The optimized geometry shows that there is large lattice expansion for the codoped anatase TiO2 due to large atomic radius of the codoped atom.The calculated substitution energies indicate that incorporation of X（X =S,Se,Te） into N-doped bulk TiO2 can not promote synergistic effect on N after substituting for Ti,whcreas it is bctter after substituting for O.According to the total density of states （DOS） and corresponding partial DOS （PDOS）,it can be seen that substituting X（X =S,Se,Te） for O,N 2p orbital is strongly hybridized with impurity states （S 3p,Se 4p,Te 5p）.After substituting X（X=S,Se,Te） for Ti,conduction band is mainly dominated by Ti 3d orbit and S 3p （Se 4p or Te 5p）-N 2p-Ti 3d hybridized states are formed.Based on Bader analysis,it can be indicated that the electron transfer is from N to X（X=S,Se,Te） if substituting X（X=S,Se,Te） for O,but it is opposite if substitute X（X=S,Se,Te） for Ti.

First-principles study on anatase TiO_2 codoped with nitrogen and praseodymium

The crystal structures, electronic structures and optical properties of nitrogen or/and praseodymium doped anatase TiO2 were calculated by first principles with the plane-wave ultrasoft pseudopotential method based on density functional theory. Highly efficient visible-light-induced nitrogen or/and praseodymium doped anatase TiO2 nanocrystal photocatalyst were synthesized by a microwave chemical method. The calculated results show that the photocatalytic activity of TiO2 can be enhanced by N doping or Pr doping, and can be further enhanced by N＋Pr codoping. The band gap change of the codoping TiO2 is more obvious than that of the single ion doping, which results in the red shift of the optical absorption edges. The results are of great significance for the understanding and further development of visible-light response high activity modified TiO2 photocatalyst. The photocatalytic activity of the samples for methyl blue degradation was investigated under the irradiation of fluorescent light. The experimental results show that the codoping TiO2 photocatalytic activity is obviously higher than that of the single ion doping. The experimental results accord with the calculated results.

Upconversion luminescence of Tm^3＋/Yb^3＋ codoped oxyfluoride glasses

Novel oxyfluoride glasses are developed with the composition of 30SiO2-15Al2O3-28PbF2-22CdF2-0.1TmF3 - xYbF3 - （4.9 - x） AlF3（x=0, 0.5, 1.0, 1.5, 2.0） in tool fraction, Furthermore, the upconversion luminescence characteristics under a 970nm excitation are investigated. Intense blue, red and near infrared luminescences peaked at 453nm, 476nm, 647nm and 789nm, which correspond to the transitions of Tm^3＋： ^1D2 →^3F4, ^1G4 →^3H6, ^1G4 →^3F4, and ^3H4 →^3H6, respectively, are observed. Due to the sensitization of Yb^3＋ ions, all the upconversion luminescence intensities are enhanced considerably with Yb^3＋ concentration increasing. The upconversion mechanisms are discussed based on the energy matching rule and quadratic dependence on excitation power. The results indicate that the dominant mechanism is the excited state absorption for those upconversion emissions.

Electronic structure and magnetic properties of(Cu,N)-codoped3C-SiC studied by first-principles calculations

The electronic structures and magnetic properties of the Cu and N codoped 3C-Si C system have been investigated by the first-principles calculation.The results show that the Cu doped Si C system prefers the anti-ferromagnetic（AFM） state.Compared to the Cu doped system,the ionicities of C–Cu and C–Si in Cu and N codoped Si C are respectively enhanced and weakened.Especially,the Cu and N codoped Si C systems favor the ferromagnetic（FM） coupling.The FM interactions can be explained by virtual hopping.However,higher N concentration will weaken the ferromagnetism.In order to keep the FM interaction,the N concentration should be restricted within 9.3% according to our analysis.

C-I codoped porous g-C_3N_4 for superior photocatalytic hydrogen evolution

Porous C‐I codoped carbon nitride materials were synthesized by in‐situ codoping with iodized ionic liquid followed by post‐thermal treatment in air.The effects of doping content of C‐I codoping with different amounts of ionic liquid on the structural,optical and photocatalytic properties of the samples were investigated.Characterization results show that more compact interlayer sacking can be achieved by post‐thermal treatment.Combined with C‐I codoping by insertion of ionic liquids,much enlarged surface area but optimized sp2 conjugated heterocyclic structure can be found in the catalysts.Optical and energy band analysis results evidence that the light absorptions especially in visible light region are significantly improved.Although the band gap of porous C‐I codoped samples enlarge because of the generation of porous,the negatively shifted conduction band position thermodynamically supplies stronger motivation for water reduction.Photoelectricity tests reveal that the photo‐induced electron density was increased after C‐I codoping modification.Also,the recombination rate of electron‐hole pairs is remarkably inhibited.The catalysts with moderate C‐I codoing content perform sharply enhanced photocatalytic H2 evolution activity under visible light irradiation.A H2 evolution rate of 168.2μmol/h was achieved and it was more than 9.8 times higher than pristine carbon nitride.This study demonstrates a novel non‐metal doping strategy for synthesis and optimization of polymer semiconductor with gratifying photocatalytic H2 evolution performance from water hydrolysis.

Enhanced Photoelectric Property of Mo-C Codoped TiO2 Films Deposited by RF Magnetron Cosputtering

Mo-C codoped TiO2 films were prepared by RF magnetron cosputtering. Ultraviolet-visible spectroscopy, atomic force microscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray Analysis and X-Ray Diffraction were used to study the influences of codoping on energy gap, surface morphology, valence states of elements, ions content and crystal structure, respectively. The concentration of photogenerated carriers was measured by studying photocurrent density, while catalytic property was evaluated by observing degradation rate of methylene blue under visible light. A Mo-doped TiO2 film, whose content of Mo had been optimized in advance, was prepared and later used for subsequent comparisons with codoped samples. The result indicates that Mo-C codoping could curtail the energy gap and shift the absorption edge toward visible range. Under the illumination of visible light, codoped TiO2 films give rise to stronger photocurrent due to smaller band gaps. It is also found that Mo, C codoping results in a porous surface, whose area declines gradually with increasing carbon content. Carbon and Molybdenum doses were delicately optimized. Under the illumination of visible light, sample doped with 9.78at% carbon and 0.36at% Mo presents the strongest photocurrent which is about 8 times larger than undoped TiO2 films, and about 6 times larger than samples doped with Mo only.

Boosting the polysulfide confinement in B/N–codoped hierarchically porous carbon nanosheets via Lewis acid–base interaction for stable Li–S batteries

Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxiety is the poor affinity toward polar polysulfides due to the intrinsic nonpolar surface of carbon.Herein, we report a direct pyrolysis of the mixture urea and boric acid to synthesize B/N–codoped hierarchically porous carbon nanosheets(B–N–CSs) as efficient sulfur host for lithium–sulfur battery. The graphene–like B–N–CSs provides high specific surface area and porous structure with abundant micropores(1.1 nm) and low–range mesopores(2.3 nm), thereby constraining the sulfur active materials within the pores. More importantly, the codoped B/N elements can further enhance the polysulfide confinement through strong Li–N and B–S interaction based on the Lewis acid–base theory. These structural superiorities significantly suppress the shuttle effect by both physical confinement and chemical interaction, and promote the redox kinetics of polysulfide conversion. When evaluated as the cathode host, the S/B–N–CSs composite displays the excellent performance with a high reversible capacity up to 772 m A h g–1 at 0.5 C and a low fading rate of ^0.09% per cycle averaged upon 500 cycles. In particular, remarkable stability with a high capacity retention of 87.1% can be realized when augmenting the sulfur loading in the cathode up to 4.6 mg cm^(-2).

NS codoped carbon nanorods as anode materials for high-performance lithium and sodium ion batteries

NS codoped carbon nanorods（NS-CNRs） were prepared using crab shell as template and polyphenylene sulfide（PPS） as both the C and S precursor, followed by carbonization in NH_3. The as-obtained NS-CNRs had a diameter of ~50 nm, length of several micrometers, and N and S contents of 12.5 at.% and 3.7 at.%,respectively, which can serve as anodes for both lithium-ion batteries（LIBs） and sodium ion batteries（SIBs）. When serving as an anode of LIB, the NS-CNRs delivered gravimetric capacities of 2154 mAh g^（-1）at current densities of 0.1 A g^（-1）and 625 mAh g^（-1）at current densities of 5.0 A g^（-1）for 1000 cycles.When serving as an anode of SIB, the NS-CNRs delivered gravimetric capacities of 303 mAh g^（-1）at current densities of 0.1 A g^（-1）and 230 mAh g^（-1）at current densities of 1.0 A g^（-1）for 3000 cycles. The excellent electrochemical performance of NS-CNRs could be ascribed to the one-dimensional nanometer structure and high level of heteroatom doping. We expect that the obtained NS-CNRs would benefit for the future development of the doped carbon materials for lithium ion batteries and other extended applications such as supercapacitor, catalyst and hydrogen storage.

(N,F)-codoped TiO_2 Nanocrystals as Visible Light-activated Photocatalyst

（N, F）-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The （N, F）- codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.

Simulation of High Power Er/Yb Codoped Fiber Linear Cavity Lasers

The performances of high power Er/Yb codoped fiber linear cavity lasers are investigated numerically. The numerical analysis is based on the iterative solution of rate equations for population density of the Er/Yb ions. The behaviors of co-pump and counter-pump methods are contrasted. Dependence of output power on input pump power, output reflectivity, operating wavelength and active fiber length is simulated, respectively. High conversion efficiency Er/Yb laser output is obtained in simulations and experiments.

N, F?Codoped Microporous Carbon Nanofibers as Efficient Metal?Free Electrocatalysts for ORR

Currently, the oxygen reduction reaction(ORR) mainly depends on precious metal platinum(Pt) catalysts. However, Pt-based catalysts have several shortcomings, such as high cost, scarcity, and poor long-term stability. Therefore, development of e cient metal-free electrocatalysts to replace Pt-based electrocatalysts is important. In this study, we successfully prepared nitrogen-and fluorinecodoped microporous carbon nanofibers(N, F-MCFs) via electrospinning polyacrylonitrile/polyvinylidene fluoride/polyvinylpyrrolidone(PAN/PVDF/PVP) tricomponent polymers followed by a hydrothermal process and thermal treatment, which was achieved for the first time in the literature. The results indicated that N, F-MCFs exhibit a high catalytic activity(E_(onset): 0.94 V vs. RHE, E_(1/2): 0.81 V vs. RHE, and electron transfer number: 4.0) and considerably better stability and methanol tolerance for ORR in alkaline solutions as compared to commercial Pt/carbon(Pt/C, 20 wt%) catalysts. Furthermore, in acidic media, N, F-MCFs showed a four-electron transfer pathway for ORR. This study provides a new strategy for in situ synthesis of N, F-MCFs as highly e cient metal-free electrocatalysts for ORR in fuel cells.

Highly Reversible Li–Se Batteries with Ultra-Lightweight N,S-Codoped Graphene Blocking Layer

The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we present a simple vacuum filtration method to synthesize nitrogen and sulfur codoped graphene(N,S-G) blocking layer, which is ultra-lightweight, conductive, and free standing. When the N,S-G membrane was inserted between the catholyte and separator, the lithium–selenium(Li–Se)batteries exhibited a high reversible discharge capacity of 330.7 mAh g^(-1) at 1 C(1 C = 675 mA g^(-1)) after 500 cycles and high rate performance(over 310 mAh g^(-1) at 4 C) even at an active material loading as high as ～5 mg cm^(-2). This excellent performance can be ascribed to homogenous dispersion of the liquid active material in the electrode, good Li^+-ion conductivity, fast electronic transport in the conductive graphene framework, andstrong chemical confinement of polyselenides by nitrogen and sulfur atoms. More importantly, it is a promising strategy for enhancing the energy density of Li–Se batteries by using the catholyte with a lightweight heteroatom doping carbon matrix.

Room-temperature anomalous Hall effect and magnetroresistance in(Ga,Co)-codoped ZnO diluted magnetic semiconductor films

This paper reports that the （Ga, Co）-codoped ZnO thin films have been grown by inductively coupled plasma enhanced physical vapour deposition. Room-temperature ferromagnetism is observed for the as-grown thin films. The x-ray absorption fine structure characterization reveals that Co2＋ and Ga3＋ ions substitute for Zn2＋ ions in the ZnO lattice and exclude the possibility of extrinsic ferromagnetism origin. The ferromagnetic （Ga, Co）-codoped ZnO thin films exhibit carrier concentration dependent anomalous Hall effect and positive magnetoresistance at room tempera- ture. The mechanism of anomalous Hall effect and magneto-transport in ferromagnetic ZnO-based diluted magnetic semiconductors is discussed.