Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

Accurate design of spatially separated double active site in Bi_(4)NbO_(8)Cl single crystal to promote Z-Scheme photocatalytic overall water splitting

The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.

Doping sites modulation of T-Nb_(2)O_(5) to achieve ultrafast lithium storage

Heteroatoms doping has been regarded as a promising route to modulate the physiochemical properties of electrode materials,in which the doping sites greatly influence the electrochemical performances.However,very few reports focus on enhancing the lithium storage performances of Nb_(2)O_(5) via heteroatoms doping,yet the effect of different doping sites remains unclear.Herein,nitrogen doping has been proposed to improve the fast-charging capability of orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))via a urea-assisted annealing process.Experimental data and theoretical calculation demonstrate that the N doping sites in T-Nb_(2)O_(5) can be tuned by the heating rate,in which substitutional N can increase the spacing of the Li^(+)transport layer as well as reduce the band gap,while interstitial N can provide an electron-rich environment for Li^(+)transport layer and then reduce the Li^(+)diffusion barrier.Arising from the synergistic effect of N doping at different sites,the N-doped T-Nb_(2)O_(5) without carbon coating delivers impressive rate performance(104.6 mA h g^(-1) at 25 C)as well as enhanced cycle stability with a retention of 70.5%over1000 cycles at 5 C.In addition,the assembled lithium ion capacitor exhibits a high energy density of46.6 Wh kg^(-1) even at high power density of 8.4 kW kg^(-1).

Fe-doped Co3O4@C nanoparticles derived from layered double hydroxide used as efficient electrocatalyst for oxygen evolution reaction

Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still remains a huge challenge. Herein, we demonstrate a feasible approach through oxidation of CoFe layered double hydroxide (CoFe-LDH) to synthesize Fe-doped Co3O4@C nanopmrticles with size of about 30-50 nm. As OER catalyst, the as-synthesized Fe-doped Co3O4@C nanoparticles exhibited superior OER performance with a small overpotential of 260 mV at the current density of 20 mA cm^-2, a small Tafel slope of 70 mV dec^-1 and long-term durability (there was no obviously OER current density degradation for 100 h) in alkaline solution. The present work opens a new avenue to the exploration of cost-effective and excellent electrocatalysts based on transition metal oxide materials to substitute precious metal materials for water splitting.

Electric and magnetic behaviour in double doped La2/3＋4x/3Sr1/3-4x/3Mn1-xMgxO3

The double-doped La2/3＋4x/3Sr1/3-4x/3Mn1-xMgxO3 samples with fixed Mn^3＋/Mn^4＋ ratio equal to 2/1 are investigated by means of magnetism and transport measurements. Phase separation is observed at temperature higher than T^onset c for x = 0.10 and 0.15. For x = 0.10, rather strong phase separation induces drastic magnetic random potential and results in the localization of carriers. Thus, the varlable-range hopping process dominates. For other samples, there is no or only weak phase separation above T^onset c. Thus, thermal activation mechanism is responsible for the high temperature transport behaviour. For x = 0.20 and 0.25, unexpected AFM behaviour is observed at low temperature. All these results are well understood by considering the special role of the ＂double-doping＂.

Layered double hydroxide-like Mg_3Al_(1–x)Fe_x materials as supports for Ir catalysts: Promotional effects of Fe doping in selective hydrogenation of cinnamaldehyde

Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg3Al)to 1(Ir/Mg3Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg3Al1–xFex support to the dispersed Ir particles and the surface geometry.

Tuning the oxygen evolution electrocatalysis on NiFe-layered double hydroxides via sulfur doping

We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni Fe-LDHs was studied and the optimal surface S content was ca. 0.43 at%. The developed S-doped Ni Fe-LDH exhibits excellent OER catalyst activity in 1.0 M KOH with overpotential of only 257 m V at the current density of 10 m A cm^-2. Moreover, the catalyst could maintain high activity after 30 h stability test. The high activity of the S-doped Ni Fe-LDH catalysts may originate from the synergistic effect between S and the Fe sites. This work provides a simple but efficient way to improve the OER performance of transition metal oxides/(oxy)hydroxides.

Identification and comparison of the local physicochemical structures of transition metal-based layered double hydroxides for high performance electrochemical oxygen evolution reactions

Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.

A continuous analytic channel potential solution to doped symmetric double-gate MOSFETs from the accumulation to the strong-inversion region

A continuous yet analytic channel potential solution is proposed for doped symmetric double-gate （DG） MOSFETs from the accumulation to the strong-inversion region. Analytical channel potential relationship is derived from the complete 1-D Poisson equation physically, and the channel potential solution of the DG MOSFET is obtained analytically. The extensive comparisons between the presented solution and the numerical simulation illustrate that the solution is not only accurate and continuous in the whole operation regime of DG MOSFETs, but also valid to wide doping concentration and various geometrical sizes, without employing any fitting parameter.

Single atom doping induced charge-specific distribution of Cu1-TiO_(2) for selective aniline oxidation via a new mechanism

Utilizing single atom sites doping into metal oxides to modulate their intrinsic active sites,achieving precise selectivity control in complex organic reactions,is a highly desirable yet challenging endeavor.Meanwhile,identifying the active site also represents a significant obstacle,primarily due to the intricate electronic environment of single atom site doped metal oxide.Herein,a single atom Cu doped TiO_(2)catalyst(Cu_(1)-TiO_(2)) is prepared via a simple“colloid-acid treatment”strategy,which switches aniline oxidation selectivity of TiO_(2) from azoxybenzene to nitrosobenzene,without using additives or changing solvent,while other metal or nonmetal doped TiO_(2) did not possess.Comprehensive mechanistic investigations and DFT calculations unveil that Ti-O active site is responsible for triggering the aniline to form a new PhNOH intermediate,two PhNOH condense to azoxybenzene over TiO_(2) catalyst.As for Cu_(1)-TiO_(2),the charge-specific distribution between the isolated Cu and TiO_(2) generates unique Cu_(1)-O-Ti hybridization structure with nine catalytic active sites,eight of them make PhNOH take place spontaneous dissociation to produce nitrosobenzene.This work not only unveils a new mechanistic pathway featuring the PhNOH intermediate in aniline oxidation for the first time but also presents a novel approach for constructing single-atom doped metal oxides and exploring their intricate active sites.

Establishment of a Parkinson’s disease model in rats via striatal one-site double injection Feasibility observation

BACKGROUND： To date, many 6-hydroxydopamine （6-OHDA）-lesioned rat models have been established by injecting 6-OHDA into two or more sites in the substantia nigra pars compacta, striatum or median forebrain bundle. The success rate of models established by this method is satisfactory, but it can raise the death rate, and is elaborate and tedious to perform. OBJECTIVE： To observe the difference between injections of 6-OHDA into the striatum from one site and two sites, and to explore the feasibility of establishing Parkinson＇s disease rat models via striatal one-site double injection. DESIGN, TIME AND SETTING： A randomized, controlled animal experiment based on a modeling comparison was performed at the Pharmacology Laboratory of Traditional Chinese Medicine, Academy of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine between August 2005 and April 2006. MATERIALS： A total of 46 male Wistar rats were purchased from Beijing Weitong Lihua Experimental Animal Technical Co., Ltd., China. 6-OHDA hydrogen bromide was sourced from Sigma Co., Ltd., USA. METHODS： All 46 rats were randomized to three groups： one-site injection （n = 18）, two-site injection （n = 18）, and control （n = 10）. Lesions in rat brains were established by infusing 5 μg 6-OHDA into the striatum at the following coordinates： anteroposterior （AP） 1.0 mm, mediolateral （ML） 2.7 mm, dorsoventral （DV）-5.2 or-6.0 mm for the one-site injection group, and AP 1.0 mm, ML 2.5 mm, DV -4.5 mm/AP-0.4 mm, ML 3.5 mm, DV-4.5 mm for the two-site injection group, respectively. Rats in the control group were injected with the same volume of 0.01% ascorbic acid as above. MAIN OUTCOME MEASURES： Tyrosine hydroxylase-positive neurons were detected by immunohistochemistry. Success rates of PD models established by one-site and two-site injection techniques were examined. RESULTS： One rat died in the one-site injection group and four in the two-site injection group. Thus behavioral testing was performed on 31 rats. There was no significant difference in the success rate of PD model establishment between one-site injection and two-site injection groups [82% （14/17） vs. 86% （12/14）, P 〉 0.05]. The numbers of tyrosine hydroxylase -positive neurons in one-site injection and two-site injection groups were not significantly different （ P 〉 0.05）, but they were significantly lower than in the control group（P 〈 0.01 ）. CONCLUSION： A Parkinson＇s disease model can be established in rats via striatal one-site double injection.

High-voltage super-junction lateral double-diffused metal-oxide semiconductor with a partial lightly doped pillar

A novel super-junction lateral double-diffused metal-oxide semiconductor （SJ-LDMOS） with a partial lightly doped P pillar （PD） is proposed. Firstly, the reduction in the partial P pillar charges ensures the charge balance and suppresses the substrate-assisted depletion effect. Secondly, the new electric field peak produced by the P/P junction modulates the surface electric field distribution. Both of these result in a high breakdown voltage （BV）. In addition, due to the same conduction paths, the specific on-resistance （Ron,sp） of the PD SJ-LDMOS is approximately identical to the conventional SJ-LDMOS. Simulation results indicate that the average value of the surface lateral electric field of the PD SJ-LDMOS reaches 20 V/μm at a 15 μm drift length, resulting in a BV of 300 V.

Properties and Application of Double Alkali Earth Doped Ce_ (0.9)Ca_(0.1-x) Sr_xO_( 1.90)

A series of solid solution material based on ceria, Ce 0.9 Ca 0.1- x Sr x O 1.90 ( x =0, 0 04, 0 05, 0 06), were synthesized by a solid reaction method. Ceria doped with two alkali earth elements has cubic fluorite structure. The ionic conductivity of these materials at high temperature was studied by impedance spectra, and an increasing effect of ionic conductivity was found. A maximum conductivity is achieved when the effective ionic radius is near to the critical radius (0 1106 nm). Some fuel cells were made using these materials as electrolyte. The output power and current of the SOFC with the electrolyte of double doped ceria are better than those of YSZ and single doped ceria, and the open circuit voltage of the double doped ceria is also higher than that of the single doped ones.

Electroluminescence of double-doped diamond thin films

A new electroluminescence device is fabricated by microwave plasma chemical vapour deposition system and electron beam vapour deposition system. It is comprised of highly doped silicon/diamond/boron/nitrogen-doped diamond/indium tin oxide thin films. Effects of process parameters on morphologies and structures of the thin films are detected and analysed by scanning electron microscopy, Raman spectrometer and x-ray photoelectron spectrometer. A direct-current （DC） power supply is used to drive the electroluminescence device. The blue light emission with a luminance of 1.2 cd·m^-2 is observed from this double-doped diamond thin film electroluminescence device at an applied voltage of 105 V.

Double-layer indium doped zinc oxide for silicon thin-film solar cell prepared by ultrasonic spray pyrolysis

Indium doped zinc oxide （ZnO：In） thin films were prepared by ultrasonic spray pyrolysis on corning eagle 2000 glass substrate. 1 and 2 at.% indium doped single-layer ZnO：In thin films with different amounts of acetic acid added in the initial solution were fabricated. The 1 at.% indium doped single-layers have triangle grains. The 2 at.% indium doped single-layer with 0.18 acetic acid adding has the resistivity of 6.82 × 10^-3 Ω. cm and particle grains. The doublelayers structure is designed to fabricate the ZnO：In thin film with low resistivity （2.58 × 10^-3 Ω. cm） and good surface morphology. It is found that the surface morphology of the double-layer ZnO：In film strongly depends on the substratelayer, and the second-layer plays a large part in the resistivity of the doublewlayer ZnO：In thin film. Both total and direct transmittances of the double-layer ZnO：In film are above 80% in the visible light region. Single junction a-Si：H solar cell based on the double-layer ZnO：In as front electrode is also investigated.

Interlayer distance effects on absorption coefficient and refraction index change in p-type double-δ-doped GaAs quantum wells

In the framework of the Thomas–Fermi(TF) approach, a model for the p-type double-δ-doped(DDD) system in Ga As is presented. This model, unlike other works in the literature, takes into account that the Poisson equation associated with the system is nonlinear. The electronic structure is calculated for heavy and light holes. The changes in the electronic structure result of the distance d between the doped layers are studied. In particular, the relative absorption coefficient as well as the relative refractive index change is calculated as a function of the incident photon energy for heavy holes. The effect of the interlayer distance exhibits, in the absorption coefficient, a red shift of the peak position and a decrease in amplitude when the distance increases. In addition, the relative refractive index change node has a red shift as well as the interlayer distance increases. The calculations show that the effect of the separation between layers has a greater influence on the linear terms. These results are very important for theoretical calculations and engineering of optical and electronic devices based in δ-doped Ga As.

Doping engineering of lithium-aluminum layered double hydroxides for high-efficiency lithium extraction from salt lake brines

Lithium-aluminum layered double hydroxides(LiAl-LDH)have been be successfully applied in commercial-scale for lithium extraction from salt lake brine,however,further advancement of their applications is hampered by suboptimal Li^(+)adsorption performance and ambiguous extraction process.Herein,a doping engineering strategy was developed to fabricate novel Zn^(2+)-doped LiAl-LDH(LiZnAl-LDH)with remarkable higher Li^(+)adsorption capacity(13.4 mg/g)and selectivity(separation factors of 213,834,171 for Li^(+)/K^(+),Li^(+)/Na^(+),Li^(+)/Mg^(2+),respectively),as well as lossless reusability in Luobupo brine compared to the pristine LiAl-LDH.Further,combining experiments and simulation calculations,it was revealed that the specific surface area,hydrophilic,and surface attraction for Li^(+)of LiZnAl-LDH were significantly improved,reducing the adsorption energy(Ead)and Gibbs free energy(ΔG),thus facilitating the transfer of Li^(+)from brine into interface followed by insertion into voids.Importantly,the intrinsic oxygen vacancies derived from Zn-doping depressed the diffusion energy barrier of Li^(+),which accelerated the diffusion process of Li^(+)in the internal bulk of LiZnAl-LDH.This work provides a general strategy to overcome the existing limitations of Li^(+)recovery and deepens the understanding of Li^(+)extraction on LiAl-LDH.

Sb^(3+)and Sm^(3+)co-doped lead-free Cs_(2)NaInCl_(6)double perovskite nanocrystals for single-component cold white emitter

Metal halide perovskites exhibit promising prospect in light-emitting diodes,solar cells,photodetectors and bioimaging.However,the workhorse of metal halide perovskites relies on toxicity lead element,which severely damages human body and environment.Among lead-free perovskites,Cs_(2)NaInCl_(6)double perovskite is one of the most promising candidates because of its great stability and easy synthesis,but suffers inadequate optical performance.Here,we doped Sb^(3+)and Sm^(3+)into Cs_(2)NaInCl_(6)nanocrystals by a hot injection method.Cs_(2)NaInCl_(6):Sb^(3+)exhibits blue emission at 447 nm.Cs_(2)NaInCl_(6):Sm^(3+),Sb^(3+)nanocrystals simultaneously generate the blue emission of Sb^(3+)and the multiple emissions of Sm^(3+)at 565,602,650 and 710 nm.With the increase of Sm^(3+)feed ratio,the emission color of Cs_(2)NaInCl_(6):Sm^(3+),Sb^(3+)gradually moves to cold white region at(0.27,0.28)in CIE chromaticity diagram and correlated color temperature of 11840 K.This work shows the potential application of Cs_(2)NaInCl_(6):Sm^(3+),Sb^(3+)nanocrystals as a single-component cold white emitter.

Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co_(2)P by rapid hydrolysis

Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.

Electronic structure regulation on layered double hydroxides for oxygen evolution reaction

Oxygen evolution reactions(OERs)as core components of energy conversion and storage technology systems,such as water splitting and rechargeable metal–air batteries,have attracted considerable attention in recent years.Transition metal compounds,particularly layered double hydroxides(LDHs),are considered as the most promising electrocatalysts owing to their unique two-dimensional layer structures and tunable components.However,heir poor intrinsic electrical conductivities and the limited number of active sites hinder their performances.The regulation of the electronic structure is an effective approach to improve the OER activity of LDHs,including cationic and anionic regulation,defect engineering,regulation of intercalated anions,and surface modifications.In this review,we summarize recent advances in the regulation of the electronic structures of LDHs used as electrocatalysts in OERs.In addition,we discuss the effects of each regulation type on OER activities.This review is expected to shed light on the development and design of effective OER electrocatalysts by summarizing various electronic structure regulation pathways and the effects on their catalytic performances.