Preparation and characterization of In and Cu co-doped ZnS photocatalysts for hydrogen production under visible light irradiation

In this work, a new photocatalyts In(0.1),Cu(x)-Zn S(x = 0.01, 0.03, 0.05) is successfully synthesized using simple hydrothermal method. The physical and chemical properties of the In and Cu co-doped Zn S photocatalyst were characterized by X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), diffuse reflectance UV-visible spectroscopy(DR UV-visible) and photoluminescence spectroscopy(PL). The photocatalytic activity of the as-prepared In and Cu co-doped Zn S for hydrogen production from water with Na_2SO_3 and Na_2S as sacrificial agent under visible light irradiation(λ ≥ 425 nm) was investigated. The presence of co-dopants facilitated the separation of electron-hole as well as increases the visible light absorption. The absorption edge of the co-doped Zn S photocatalyst shifted to longer wavelength as the amount of Cu increases. This indicates that the absorption properties depended on the amount of Cu doped. The photocatalytic activity of single doped In(0.1)-Zn S was significantly enhanced by co-doping with Cu under visible light irradiation. The highest photocatalytic activity was observed on In(0.1),Cu(0.03)-Zn S with the hydrogen production rate of 131.32 μmol/h under visible light irradiation.This is almost 8 times higher than single doped In(0.1)-ZnS.

Ti, Zn co-doped hematite photoanode for solar driven photoelectrochemical water oxidation

Although there have been many reports of metal doping to ameliorate the drawbacks of hematite as the photoanode for water oxidation, most of them focused on monometallic doping, and only a few of them payed attention to bimetallic doping. What is worse, the synergetic mechanism between two metal dopants was not sufficiently studied, especially the density functional theory(DFT) calculation. In this work, the n-type hematite was synthesized by introducing Ti dopant into hematite through the hydrothermal method, and dipping-sintering treatment was employed to further introduce homogeneously dispersed Zn dopant into that, forming the Ti, Zn co-doped hematite. Under the optimal condition, Tidoped hematite photoanode reached approximately 2-times enhancement of the photocurrent density compared with the pristine one at 1.23 V vs. RHE, while Ti, Zn co-doped hematite anode obtained another25% elevation. UV–Vis spectroscopy, Mott–Schottky plots, EIS analysis, photo-oxidation of hole scavenger(H2O2), and DFT calculation were employed to understand the role of Ti, Zn dopant. Based on the obtained results, the synergetic mechanism of two dopants was discussed, i.e., the improvement of PEC performance of Ti, Zn co-doped hematite photoanode was possibly attributed to greater carrier density and improved charge separation efficiency at the surface of hematite. This work provides new strategy and understanding of the improvement of PEC performance of hematite by doping engineering.

Construction of Cu-Zn Co-doped layered materials for sodium-ion batteries with high cycle stability

Due to its high operational voltage and energy density,P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) has become a leading cathode material for sodium-ion batteries(SIBs),which is an ideal option for large-scale energy storage.However,the practical application of P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) is limited by the capacity constraints and unwanted phase transitions,presenting significant challenges to the widespread application of SIBs.To address these challenges and optimize the electrochemical properties of the P2 phase cathode material,this study proposes a Cu and Zn co-doped strategy to improve the electrochemical performance.The incorporation of Cu/Zn can stabilize the P2-phase structure against P2-O2 phase transitions,thus enhancing its electrochemical properties.The as-obtained P2-type Na0.67[Ni_(0.3)Mn_(0.58)Cu_(0.09)Zn_(0.03)]O_(2) cathode material shows an impressive cycling stability,maintaining 80%capacity retention after 1000 cycles at 2 C.The cyclic voltammetry(CV)tests show that the Cu^(2+)/Cu^(3+)redox reaction is also involved in charge compensation during the charge/discharge process.

Manipulating Na occupation and constructing protective film of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2) as long-term cycle stability cathode for sodium-ion batteries

P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O_(2)phase transformation,Na+/vacancy ordering,and transition metal(TM)dissolution seriously damage its cycling stability and restrict its commercialization process.Herein,Na occupation manipulation and interface stabilization are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and introducing lithium difluorophosp(LiPO_(2)F_(2))film-forming electrolyte additive.The Zn/Ti co-doping regulates the occupancy ratio of Nae/Nafat Na sites and disorganizes the Na+/vacancy ordering,resulting in a faster Na+diffusion kinetics and reversible P2-Z phase transition for P2-Na_(0.67)Ni_(0.28)Zn_(0.05)Mn_(0.62)Ti_(0.05)O_(2)(NNZMTO).Meanwhile,the LiPO_(2)F_(2)additive can form homogeneous and ultrathin cathode-electrolyte interphase(CEI)on NNZMTO surface,which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution,surface structure transformation,and micro-crack generation.Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mechanism of NNZMTO with Li PO_(2)F_(2)additive.As a result,the NNZMTO displays outstanding capacity retention of 94.44%after 500 cycles at 1C with 0.3 wt%Li PO_(2)F_(2),excellent rate performance of 92.5 mA h g^(-1)at 8C with 0.1 wt%Li PO_(2)F_(2),and remarkable full cell capability.This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials,which provides a promising direction for developing high-performance cathodes for SIBs.

Enhanced activity of ZnS(111) by N/Cu co-doping:Accelerated degradation of organic pollutants under visible light

High-efficiency photocatalysts are of great significance for the application of photocatalytic technology in water treatment.In this study,N/Cu co-doped ZnS nanosphere photocatalys(N/Cu-ZnS) is synthesized by a hydrothermal method for the first time.After doping,the tex ture of nanosphere becomes loose,the nanometer diameter is reduced,making the specific surface area of catalyst increased from 34.73 to 101.59 m^(2)/g.The characterization results show that more ZnS (111) crystal planes are exposed by N/Cu co-doping;the calculations of density functional theory show that N/Cu co-doping can increase the catalytic activity of the ZnS (111) crystal plane,enhance the adsorption capacity of (111) crystal plane to O_(2)and promote the generation of·O_(2)-.The energy levels of the introduced impurities can be hybridized with the energy levels of S and Zn at the top of valence band and the bottom o conduction band,which makes the band gap narrower,thus enhancing the absorption o visible light.Compared with pure ZnS,the degradation rates of 2,4-dichlorophenol (2,4-DCP and tetracycline (TC) by N/Cu-ZnS under visible light (>420 nm) are increased by 83.7 and51 times,respectively.In this research,a promising photocatalyst for photocatalytic degra dation of organic pollutants in wastewater is provided.

Tunable luminescence in co-doped Zn3Al2Ge2O10:Cr3+by controlling crystal field splitting and nephelauxetic effect

Ce3+/Dy3+/Tb3+/Eu3+/Mn2+and Cr3+ions co-doped Zn3 Al2 Ge2 O10 phosphor were prepared by a hightemperature solid-state method.X-ray diffraction patterns prove the cubic phase structure of prepared Zn3 Al2 Ge2 O10 phosphor,Emission,excitation spectra and decay curves confirm the tunable luminescence.Different degrees of the decrease of emission FWHM in Zn3 Al2 Ge2 O10:0.02 Cr3+,RE(RE=Ce3+,Dy3+,Tb3+,Eu3+)and Zn3 Al2 Ge2 O10:0.02 Cr3+,Mn2+are observed.The reason of variable FWHM is the effect of crystal field splitting and nephelauxetic effect,and the nephelauxetic effect is dominant.Therefore,the emission FWHM decreases with the increasing concentration of Mn2+/Tb3+/Eu3+in Zn3 Al2 Ge2 O10:0.02 Cr3+,and for Zn3 Al2 Ge2 O10:0.02 Cr3+,Ce3+and Zn3 Al2 Ge2 O10:0.02 Cr3+,Dy3+,it is a constant.The variation of Zn3 Al2 Ge2 O10:0.02 Cr3+,Tb3+is more obvious than that of Zn3 Al2 Ge2 O10:0.02 Cr3+,Eu3+,because Tb3+ion has smaller electronegativity.Thus,the tunable luminescence of Cr3+can be realized by co-doping different ions.And these phosphors have potential applications in light-emitting diodes for plant growth.

Zn and Ag Co-doped Anti-microbial TiO_2 Coatings on Ti by Micro-arc Oxidation

Micro-porous TiO2 coatings co-doped with Zn^2＋ and Ag nanoparticles were fabricated on Ti by microarc oxidation （MAO） for 0.5, 1.5, 2 and 4 min, respectively. The evolutions of morphology and phase component of the coating as a function of processing time were investigated. The microstructure of the 2 min treated coating was further observed by transmission electron microscopy to explore the coating formation mechanism. The amounts of Ag and Zn released from the 2 min treated coating were measured and the antibacterial properties of the coatings against Staphylococcus aureus （S. aureus） were also investigated. The obtained results showed that with prolonged MAO time, the contents of Ag and Zn on the coating surfaces increased. All the coatings were micro-porous with pore diameters of 1 -4μm; however, some pores were blocked by deposits on the 4 min treated coating. The 2 rain treated coating was composed of amorphous TiO2, anatase, futile, ZnO, Zn2TiO4 and homogenously distributed Ag nanoparticles. After immersion, Zn^2＋, Ag^＋, Ti^2＋ and Ca^2＋ were released from the coating and with the immersion time prolonged, the accumulated concentrations of these ions increased. After immersion for 36 weeks, the accumulated Zn2. and Ag^＋ concentrations were 6.88 and 0.684 ppm, respectively, which are higher than the minimal inhibitory concentration but much lower than the cytotoxic concentration. Compared with polished Ti control, the coatings co-doped with Zn^2＋ and Ag nanoparticles significantly inhibited the ad- hesions of S. uureus and reduced the amounts of planktonic bacteria in culture medium, indicating that the Zn and Ag co-doped TiO2 could be a bio-adaptable coating for long-lasting anti-microbial performance.

Synergistic combination of a Co-doped𝜎σ-MnO_(2)cathode with an electrolyte additive for a high-performance aqueous zinc-ion battery

The key challenges in aqueous zinc-manganese dioxide batteries(MnO_(2)//Zn)are their poor electrochemical kinetics and stability,which are mainly due to low conductivity and the inevitable dissolution of MnO_(2).A syn-ergistic combination of a Co-doped𝜎σ-MnO_(2)electrode(Co-MnO_(2))and a Co(CH_(3)COO)_(2)•4H_(2)O(CoAc)electrolyte additive is here developed to design a high-performance aqueous MnO_(2)//Zn battery(denoted as a Co-MnO_(2)//Zn battery with CoAc).The introduction of Co ions(Co^(3+)/Co^(2+))into the𝜎σ-MnO_(2)electrode is achieved via a facile one-step electrodeposition method.Benefitting from the synergistic coupling effect of the Co-MnO_(2)electrode and the CoAc electrolyte additive,the fabricated Co-MnO_(2)//Zn battery with CoAc shows a commendable dis-charge capacity of 313.8 mAh g^(−1)at 0.5 A g^(−1),excellent rate performance,excellent durability over 1000 cycles(∼92%capacity retention at 1.0 A g^(−1))and admirable energy density(439.3 Wh kg^(−1)),which is a significant improvement compared with an un-doped𝜎σ-MnO_(2)//Zn battery.

Compensation of Zn substitution and secondary phase controls effective mass and weighted mobility in In and Ga co-doped ZnO material

Conductivity s and thermal conductivity k are directly related to carrier concentration while Seebeck coefficient S is inversely proportional to carrier concentration.Therefore,improving thermoelectric(TE)performance is challenging.Here,the first-time analysis of secondary phase-controlled TE performance in terms of density-of-state effective mass m*d,weighted mobility mw and quality factor B is discussed in ZnO system.The results show that the secondary spinel phase Ga2O_(3)(ZnO)9 not only impacts on k but also on s and S at high temperature,while the effect of carrier concentration seem to be dominant at low temperature.For the high-spinel-segregation sample,a compensation of dopant atoms from the spinel to substitutional sites in the ZnO matrix at high temperature leads to a low decreased rate of temperaturedependent m*d.The compensation process also induces a band sharpening,a small mw reduction,and a large B enhancement.As a result,In and Ga co-doped ZnO bulk with the highest spinel segregation achieves the greatest PF improvement by 112.8%,owing to enhanced Seebeck coefficient by 110%as compared to the good Zn-substitution sample.