Ba0.85Ca0.15Ti0.9Zr0.1O3 （BCTZ） lead-free piezoelectric ceramics co-doped with CeO2 （x=0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%） and Li2CO3 （0.6 wt.%） were prepared by conventional solid-state reaction m...Ba0.85Ca0.15Ti0.9Zr0.1O3 （BCTZ） lead-free piezoelectric ceramics co-doped with CeO2 （x=0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%） and Li2CO3 （0.6 wt.%） were prepared by conventional solid-state reaction method. Influence of CeO2 doping amount on the piezoelectric properties, dielectric properties, phase composition and microstructure of prepared BCTZ lead-free piezoelectric ceramics doped with Li2CO3 were investigated by X-ray diffraction （XRD） and scanning electron microscopy （SEM） and other analytical methods. The results showed that the sintered temperature of BCTZ lead-free piezoelectric ceramics doped with CeO2 decreased greatly when Li2CO3 doping amount was 0.6 wt.%;a pure perovskite structure of BCTZ lead-free piezoelectric ceramics co-doped with Li2CO3 and CeO2 and sintered at 1050 ℃ could also be obtained. The piezoelectric constant （d33）, the relative permit-tivity （εr） and the planar electromechanical coupling factor （kp） of BCTZ ceramics doped with Li2CO3 increased firstly and then de-creased, the dielectric loss （tanδ） decreased firstly and then increased and decreased at last when CeO2 doping amount increased. The influence of CeO2 doping on the properties of BCTZ lead-free piezoelectric ceramics doped with Li2CO3 were caused by“soft effect”and “hard effect”piezoelectric additive and causing lattice distortion. When CeO2 doping amount （x） was 0.2 wt.%, the BCTZ ceramics doped with Li2CO3 （0.6 wt.%） and sintered at 1050 ℃ possessed the best piezoelectric property and dielectric property with d33 of 436 pC/N, kp of 48.3%,εr of 3650, tanδof 1.5%.展开更多
Quinary system piezoelectric ceramics PSN-PZN-PMS-PZT were prepared by using a two-step method. The effects of CeO2 doping on piezoelectric and dielectric properties of the system were investigated at morphotropic pha...Quinary system piezoelectric ceramics PSN-PZN-PMS-PZT were prepared by using a two-step method. The effects of CeO2 doping on piezoelectric and dielectric properties of the system were investigated at morphotropic phase boundary （MPB）. The results reveal that the relative dielectric constant ε33^T｜ε0, the Curie temperature To, the piezoelectric constant d33, the mechanical quality factor Qm, and the electromechanical coupling coefficient Kp are changed with the increase of CeO2 content. On the other hand, the effects of CeO2 doping on the dielectric properties of PSN-PZN-PMS-PZT piezoelectric ceramics at high electric field are consistent with the change at weak electric field. The values of dielectric constant and dielectric loss are enhanced with the increasing of electric field.展开更多
Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied ...Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.展开更多
The development of optoelectronic technologies demands photodetectors with miniaturization,broadband operation,high sensitivity,and low power consumption.Although 2D van der Waals(vd W)heterostructures are promising c...The development of optoelectronic technologies demands photodetectors with miniaturization,broadband operation,high sensitivity,and low power consumption.Although 2D van der Waals(vd W)heterostructures are promising candidates due to their built-in electric fields,ultrafast photocarrier separation,and tunable bandgaps,defect states limit their performance.Therefore,the modulation of the optoelectronic properties in such heterostructures is imperative.Surface charge transfer doping(SCTD)has emerged as a promising strategy for non-destructive modulation of electronic and optoelectronic characteristics in two-dimensional materials.In this work,we demonstrate the construction of high-performance p-i-n vertical heterojunction photodetectors through SCTD of MoTe_(2)/ReS_(2)heterostructure using p-type F_(4)-TCNQ.Systematic characterization reveals that the interfacial doping process effectively amplifies the built-in electric field,enhancing photogenerated carrier separation efficiency.Compared to the pristine heterojunction device,the doped photodetector exhibits remarkable visible to nearinfrared(635-1064 nm)performance.Particularly under 1064 nm illumination at zero bias,the device achieves a responsivity of 2.86 A/W and specific detectivity of 1.41×10^(12)Jones.Notably,the external quantum efficiency reaches an exceptional value of 334%compared to the initial 11.5%,while maintaining ultrafast response characteristics with rise/fall times of 11.6/15.6μs.This work provides new insights into interface engineering through molecular doping for developing high-performance vd W optoelectronic devices.展开更多
Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods...Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods were used as supports to prepare MnOx/CeO2‐NR, MnOx/CZ‐NR, MnOx/CA‐NR, and MnOx/CS‐NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high‐resolution TEM, X‐ray diffraction, Raman and N2‐physisorption analyses, hydrogen temperature‐programmed reduction, ammonia temperature‐programmed desorption, in situ diffuse reflectance infrared Fourier‐transform spectroscopic analysis of the NH3 adsorption, and X‐ray photoelectron spectroscopy. Moreover, the catalytic performance and H2O+SO2 tolerance of these samples were evaluated through NH3‐selective catalytic reduction (NH3‐SCR) in the absence or presence of H2O and SO2. The obtained results show that the MnOx/CS‐NR catalyst exhibits the highest NOx conversion and the lowest N2O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn4+ content, and the lowest redox ability. The MnOx/CS‐NR catalyst also presents excellent resistance to H2O and SO2. All of these phenomena suggest that Si4+ is the optimal dopant for the MnOx/CeO2‐NR catalyst.展开更多
Doping of different rare-earth metals （Pr, Nd, Y and La） had an evident influence on the catalytic performance of CuO-CeO2 for the preferential oxidation （PROX） of CO in excess hydrogen. As for Pr, the doping enha...Doping of different rare-earth metals （Pr, Nd, Y and La） had an evident influence on the catalytic performance of CuO-CeO2 for the preferential oxidation （PROX） of CO in excess hydrogen. As for Pr, the doping enhanced the catalytic activity of CuO-CeO2 for PROX. For example, the CO conversion over the above catalyst for PROX was higher than 99% at 120 °C. Especially, the doping of Pr widened the temperature window by 20 °C over CuO-CeO2 with 99% CO conversion. For Nd, Y, and La, the doping depressed the catalytic activity of CuO-CeO2 for PROX. However, the doping of transition metals markedly improved the selectivity of CuO-CeO2 for PROX.展开更多
All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercializat...All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.展开更多
To improve the oxidation resistance of HfB_(2)-SiC coatings on carbon/carbon composites at 1700°C in air,CeO_(2) was introduced to improve oxygen blocking and its mechanism was investigated.During the rapid oxida...To improve the oxidation resistance of HfB_(2)-SiC coatings on carbon/carbon composites at 1700°C in air,CeO_(2) was introduced to improve oxygen blocking and its mechanism was investigated.During the rapid oxidation stage,CeO_(2) accelerated the formation of a multiphase glass layer on the coating surface.The maximum oxidation rates of CeO_(2)-HfB2-SiC coatings with 1%,3%,and 5%CeO_(2) were 24.1%,20.3%,and 53.2%higher than that of the unmodified HfB2-SiC coating,respectively.In the stable oxidation stage,the maximum oxidation rates of coatings with 1%and 3%CeO_(2) decreased by 31.4%and 21.9%,respectively,demonstrating adequate inert protection.CeO_(2) is a“coagulant”and“stabilizer”in the composite glass layer.However,increasing the CeO_(2) content accelerates the reaction between the SiO_(2) glass phase and SiC,leading to a higher SiO_(2) consumption and reduced self-healing ability of the glass layer.The 1%CeO_(2)-60%HfB2-39%SiC coating showed improved glass layer viscosity and stability,moderate SiO_(2) consumption,and better self-healing ability,significantly boosting the oxidation protection of the coating.展开更多
LiNiO_(2)(LNO)is one of the most promising cathode materials for lithium-ion batteries.Tungsten element in enhancing the stability of LNO has been researched extensively.However,the understanding of the specific dopin...LiNiO_(2)(LNO)is one of the most promising cathode materials for lithium-ion batteries.Tungsten element in enhancing the stability of LNO has been researched extensively.However,the understanding of the specific doping process and existing form of W are still not perfect.This study proposes a lithium-induced grain boundary phase W doping mechanism.The results demonstrate that the introduced W atomsfirst react with the lithium source to generate a Li–W–O phase at the grain boundary of primary particles.With the increase of lithium ratio,W atoms gradually diffuse from the grain boundary phase to the interior layered structure to achieve W doping.The feasibility of grain boundary phase doping is verified byfirst principles calculation.Furthermore,it is found that the Li2WO4 grain boundary phase is an excellent lithium ion conductor,which can protect the cathode surface and improve the rate performance.The doped W can alleviate the harmful H2↔H3 phase transition,thereby inhibiting the generation of microcracks,and improving the electrochemical performance.Consequently,the 0.3 wt%W-doped sample provides a significant improved capacity retention of 88.5%compared with the pristine LNO(80.7%)after 100 cycles at 2.8–4.3 V under 1C.展开更多
Cerium oxide is an earth-abundant,highly researched multifunctional oxide with great technological importance and wide applications area.Trivalent rare earth(RE^(3+))dopants modify the defects concentration,create ple...Cerium oxide is an earth-abundant,highly researched multifunctional oxide with great technological importance and wide applications area.Trivalent rare earth(RE^(3+))dopants modify the defects concentration,create plenty of Ce^(3+)■Ce^(4+)redox centres and generate numerous oxygen vacancies than the pure ceria.In the present work,CeO_(2)(CE),10 mol%Gd doped ceria(Ce_(0.9)Gd_(0.1)O_(2-δ);CGO),and 10 mol%Sm doped ceria(Ce_(0.9)Sm_(0.1)O_(2-δ);CSO)were synthesized by sol-gel auto-combustion method.The phase formation,particle morphology,and elemental distribution of the synthesized powder samples were studied by X-ray diffraction,Fourier transform infrared spectroscopy,field emission scanning electron microscopy,and energy dispersive X-ray analysis.UV-diffuse reflectance spectroscopy was used to study the optical properties of the material.The band gaps of the CE,CSO and CGO were calculated to be2.81,2.71 and 2.60 eV,respectively.Electrochemical impedance spectroscopy(EIS)at room temperature(RT)investigated the materials'electrical properties.The improved electrical conductivity was registered for the doped variants.CGO reaches the highest one(0.4×10^(-7)S/cm)at RT.Cyclic voltammetry(CV)was performed to study the oxidation-reduction behavior and reversibility of the ion intercalation-deintercalation process of the materials in an electrolyte solution.For the doped ceria,a threefold improved current density is observed for the cathodic part,while a small improvement is reflected in the anodic part.Specific capacitance(C_(sp))was calculated at the Faradaic and non-Faradaic region of the voltammograms.C_(sp)of the materials increases in the order of CE<<CSO<CGO.The highest Csp 345.16 F/g at a scan rate of 5 mV/s is obtained for the CGO.Lastly,a correlation is drawn by analysing cyclic voltammograms to conclude the applicability of the doped ceria material for roomtemperature water-electrolysis in the alkaline medium.展开更多
There has been a continuous effort to improve the thermal stability of subnanometric platinum(Pt)cluster(<2 nm) catalyst because Pt cluster on CeO_(2) support can be mobile and aggregated into nanoparticle on heati...There has been a continuous effort to improve the thermal stability of subnanometric platinum(Pt)cluster(<2 nm) catalyst because Pt cluster on CeO_(2) support can be mobile and aggregated into nanoparticle on heating at elevated temperatures,yet this great challenge remains.In this study,a strategy is reported to improve the thermal stability of subnanometric Pt cluster by hydrothermal deposition method.Based on this method,zirconium(Zr) was precisely doped on surface of Ce_(0.95)Zr_(0.05)O_(2) by accurately controlling Pt subnanometric cluster size.The surface doping of Zr is favorable for forming the Zr-O-Ce site and activating surface lattice oxygen atoms,which results in strong electronic interactions to stabilize the Pt subnanometric cluster.After high-temperature aging treatment at 1000℃/4 h,the single atom Pt supported on CeO_(2) is aggregated into larger sized(>3 nm) nanoparticle.In contrast,the single atom Pt supported on Ce_(0.95)Zr_(0.0)5O_(2) displays less agglomeration into subnanometric cluster with size of(1.4±0.3) nm.Moreover,the CO oxide catalytic performance of Ce_(0.95)Zr_(0.0)5O_(2)-Pt is 26% and 31%higher than that of CeO_(2)-Pt and commercial Al_(2)O_(3)-Pt catalysts,respectively.The experimental and density functional theory(DFT) calculations indicate that the Zr-O-Ce site and Pt subnanometric cluster interface have more defect sites and active oxygen species than CeO_(2)-Pt interface,which activate the Mars van Krevelen(MvK) mechanism,facilitating the catalytic performance.展开更多
Integrating electrocatalytic and photocatalytic functionalities into a single-component system offers a promising strategy for enhancing catalytic activity in photo-assisted electrocatalysis.This synergy is critical f...Integrating electrocatalytic and photocatalytic functionalities into a single-component system offers a promising strategy for enhancing catalytic activity in photo-assisted electrocatalysis.This synergy is critical for advancing energy conversion efficiency,yet significant challenges persist,particularly in optimizing individual layers and minimizing charge recombination.In this work,we present a novel singlecomponent photo-assisted electrocatalytic system based on Ni-or Co-doped CeO_(2),which simultaneously functions as a light absorber and electrocatalyst.We elucidate the critical relationship between bandgap engineering and d-band states,demonstrating that controlled modulation of dopant-derived 3d states within the CeO_(2)bandgap facilitates visible-light harvesting and optimizes the adsorption energetics of key reaction intermediates.Specifically,Ni-doped CeO_(2)introduces additional 3d states near the Fermi level,narrowing the bandgap from 3.0 to 2.7 eV.This modification not only enhances visible-light absorption but also improves charge transfer efficiency at the catalyst-electrolyte interface.Density functional theory(DFT)calculations and spectroscopic analyses reveal that Ni doping significantly enhances performance,achieving a 64 mV reduction in overpotential at 50 mA/cm^(2)under illumination,while Co-doped CeO_(2)exhibits a 35 mV reduction in 1 M NaOH.Our findings demonstrate that a simple doping strategy can tailor 3d states to promote efficient charge carrier separation and intermediate transfer,offering a versatile and scalable approach to designing advanced electrocatalysts for water splitting.展开更多
In this work,the rare-earth doped ternary lead zirconate titanate ceramics with chemical formula of[0.3 Pb(Zn_(1/3)Nb_(2/3))O_(3)-0.7Pb(Zr_(0.52)Ti_(0.48))O_(3)]+x wt%CeO_(2)(x=0-0.5,abbreviated as 0.3PZN-0.7PZT-xCe)w...In this work,the rare-earth doped ternary lead zirconate titanate ceramics with chemical formula of[0.3 Pb(Zn_(1/3)Nb_(2/3))O_(3)-0.7Pb(Zr_(0.52)Ti_(0.48))O_(3)]+x wt%CeO_(2)(x=0-0.5,abbreviated as 0.3PZN-0.7PZT-xCe)were synthesized by a conventional solid-state reaction route,specific attentions was focused on the effects of CeO_(2)dopants on the structures and electrical properties of the 0.3PZN-0.7PZT ceramics,revealing the role conve rsion of CeO_(2)dopants with its doping amount(x).When less CeO_(2)(x≤0.2)is introduced into 0.3PZN-0.7PZT,the prepared ceramics are identified as the coexistence of rhombohedral and tetragonal phases,also involved with an increased grain size and a reduced atomic ratio of Pb/(Zr+Ti+Zn+Nb).The increased remanent polarization(Pr)and deceased coercive filed(Ec),as well as improved dielectric permittivity(er)and piezoelectric coefficient(d_(33))de monstrate the donor substitution of Ce^(3+)for Pb^(2+)at the A-site of perovskite lattice.Conversely,the introduction of excessive CeO_(2)(x>0.2)causes a reversal evolution in the electrical properties of ceramics,suggesting that some of the introduced cerium element tends to become Ce4+,which equivalently substitutes for Zr^(4+)at the B-site.Additionally,the diffused phase transition(DPT)behaviors of the 0.3PZN-0.7PZT-xCe ceramics were investigated by the modified Curie-Weiss Law.The sample with x=0.2 shows reduced DPT character and optimized electrical properties,including TC=297℃,εr=1400,d_(33)=480 pC/N,tanδ=1.6%,kp=65%,d_(33)·g_(33)=16.32×10^(-12)m^(2)/N,Pr=38.3μC/cm^(2)and Ec=1.02 kV/mm.These enhanced electrical properties not only are contributed by the donor substitution effect of Ce^(3+),but also benefit from the optimized morphotropic phase boundary that is close to the tetragonal-rich side.展开更多
Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,preci...Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based catalysts.Herein,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO_(2)nanorods were effectively created,with adjustable vacancy/Cu ratio.The resulting optimum catalyst shows up to 79%catalytic current density to hydrocarbons(excluding CO),with 49%faradaic efficiency to CH4.Experiments and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to hydrocarbons.These findings may spur new insights for designing and developing more controllable chemical process relevant to CO_(2)utilization.展开更多
Nitrogen dioxide(NO_(2))is a significant air pollutant with harmful effects on human health and the environment.Timely and accurate monitoring of NO_(2)concentrations is crucial for improving air quality and protectin...Nitrogen dioxide(NO_(2))is a significant air pollutant with harmful effects on human health and the environment.Timely and accurate monitoring of NO_(2)concentrations is crucial for improving air quality and protecting public health.However,quantifying NO_(2)in the presence of other gases remains challenging.Herein,we integrate Ru onto the MoS_(2)surface to form Ru-S-Mo active sites,thereby tuning the electronic structure of MoS_(2)for enhanced NO_(2)detection.This sensor shows excellent sensitivity(29.7%at 100×10^(-6)NO_(2)and 25℃),with a linear response to NO_(2)ranging from 0.5 to 200×10^(-6),and a significantly reduced response/recovery time from 160/3636 s for pure MoS_(2)to 58/427 s for Ru@MoS_(2)at 100×10^(-6)NO_(2).Additionally,the sensor is highly selective for NO_(2),exhibiting a response 14 times higher than for other gases,and possesses strong anti-interference capabilities,accurately quantifying NO_(2)in the presence of varying H_(2)concentrations(10×10^(-6)-200×10^(-6))with a low RSD of 5.34%.A portable wireless NO_(2)monitoring system was successfully constructed using Ru@MoS_(2),enabling real-time gas leak detection(10×10^(-6)-50×10^(-6))with hazard warnings and maintaining a stable response to NO_(2)over a 4-week period.This work extends the gas sensing applications of MoS_(2)and provides a portable,wireless,and high-selectivity NO_(2)sensing method for environmental monitoring and safety assurance.展开更多
The poor corrosion resistance of magnesium(Mg)and its alloys limits their application in various fields.Micro arc oxidation(MAO)coatings can improve the corrosion resistance,but the pore defects and low surface hardne...The poor corrosion resistance of magnesium(Mg)and its alloys limits their application in various fields.Micro arc oxidation(MAO)coatings can improve the corrosion resistance,but the pore defects and low surface hardness make them susceptible to wear and accelerated corrosion during usage.In this study,a ZrO_(2)nanoparticles doped-MAO coating is prepared on the ZK61 Mg alloy by utilizing an MgF_(2)passivation layer to prevent ablation.The ZrO_(2)nanoparticles re-melt and precipitate due to local discharging,which produces evenly dispersed nanocrystals in the MAO coating.As a result,the hardness of the MAO coating with the appropriate ZrO_(2)concentration increases by over 10 times,while the wear rate decreases and corrosion resistance increases.With increasing ZrO_(2)concentrations,the corrosion potentials increase from−1.528 V of the bare ZK61 Mg alloy to−1.184 V,the corrosion current density decreases from 1.065×10^(–4)A cm^(–2)to 3.960×10^(–8)A cm^(–2),and the charge transfer resistance increases from 3.41×10^(2)Ωcm^(2)to 6.782×10^(5)Ωcm^(2).Immersion tests conducted in a salt solution for 28 d reveal minimal corrosion in contrast to severe corrosion on the untreated ZK61 Mg alloy.ZrO_(2)nanoparticles improve the corrosion resistance of MAO coatings by sealing pores and secondary strengthening of the corrosion product layer.展开更多
PrBaFe_(2)O_(5+δ)(PBF)is one of the promising cathode materials for intermediate-temperature solid oxide fuel cell(IT-SOFC)technology.However,as the operating temperature decreases,the electrochemical performance of ...PrBaFe_(2)O_(5+δ)(PBF)is one of the promising cathode materials for intermediate-temperature solid oxide fuel cell(IT-SOFC)technology.However,as the operating temperature decreases,the electrochemical performance of this material deteriorates rapidly.To counter this,various doping strategies have been tested and reported in order to improve the electrochemical properties of this material at intermediate-temperatures.In this study,Mg-doping to partially substitute Fe of PBF was investigated.PrBaFe_(2-x)Mg_(x)O_(5+δ)(PBFMgx,x=0.1,0.15,0.2,0.3)materials were successfully synthesized,and their electrochemical performance as IT-SOFC cathode was evaluated.It is shown that Mg-doping enhances the conductivity of PBF between 650 and 800℃,impacts little on the area-specific resistance of oxygen reduction reaction at and above 700℃,and,most significantly,improves the power density of the NiSDC/SDC/PBFMg0.15single cell by 52%compared to the un-doped PBF.This enhanced electrochemical performance is attributed to the improvement in PBF conductivity by Mg-doping.展开更多
Water purification systems based on transition metal dichalcogenides face significant challenges,including lack of reactivity under dark conditions,scarcity of catalytically active sites,and rapid recombination of pho...Water purification systems based on transition metal dichalcogenides face significant challenges,including lack of reactivity under dark conditions,scarcity of catalytically active sites,and rapid recombination of photogenerated charge carriers.Simultaneously increasing the number of active sites and improving charge separation efficiency has proven difficult.In this study,we present a novel approach combining molybdenum(Mo) monoatomic doping and size engineering to produce a series of Mo-ReS_(2) quantum dots(MR QDs) with controllable dimensions.High-resolution structural characterization,first-principle calculations,and piezo force microscopy reveal that Mo monoatomic doping enhances the lattice asymmetry,thereby improving the piezoelectric properties.The resulting piezoelectric polarization and the generated built-in electric field significantly improve charge separation efficiency,leading to optimized photocatalytic performance.Additionally,the doping strategy increases the number of active sites and improves the adsorption of intermediate radicals,substantially boosting photo-sterilization efficiency.Our results demonstrate the elimination of 99.95% of Escherichia coli and 100.00% of Staphylococcus aureus within 30 min.Furthermore,we developed a self-purification system simulating water drainage,utilizing low-frequency water streams to trigger the piezoelectric behavior of MR QDs,achieving piezoelectric synergistic photodegradation.This innovative approach provides a more environmentally friendly and economical method for water self-purification,paving the way for advanced water treatment technologies.展开更多
Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),Cr...Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),CrS_(2)with one S vacancy(v-CrS_(2)), and Ti doped CrS_(2)(Ti@CrS_(2)). The results have shown that the pristine CrS_(2)exhibits inert character for NO activation. However, v-CrS_(2)and Ti@CrS_(2)can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates(0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts(-0.96~-1.64 e V), compared to the situation of CrS_(2)(0.065 e/-0.30 e V). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS_(2)and Ti@CrS_(2)all exhibit ultralow limiting potentials of-0.03~-0.47 V, following both*NOH and*NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.展开更多
Zn-N_(2)batteries,which are comprised of nitrogen reduction reaction(NRR)and oxygen evolution reaction(OER),represent an emerging technology for efficient ammonia production and simultaneous power generation.Neverthel...Zn-N_(2)batteries,which are comprised of nitrogen reduction reaction(NRR)and oxygen evolution reaction(OER),represent an emerging technology for efficient ammonia production and simultaneous power generation.Nevertheless,the intrinsic limitations of NRR and OER currently preclude its advancement.In this paper,Co and B co-doped Lavoisier framework series materials(MIL)are synthesized.Rapid mass transfer is rendered feasible with B_(0.25)-MIL-88-Fe_(4)Co_(1) by the distinctive double cone microrods structure.The addition of soft acid metal node Co^(2+)and B with defective electronic structure modifies the electronic configuration of MIL-88-Fe.At the same time,doping causes defects in the metal-organic frameworks,expands effectively the pore size,and increases the specific surface area,thereby expediting the adsorption of N_(2)and the release of O_(2).The electrocatalysis results show that the dual-doping scheme increases the NH_(3)yield(127.27μg^(-1)h^(-1)mg_(cat)^(-1))and Faraday efficiency(25.81%)while reducing the overpotential of OER(330 mV),achieving a power density of 8.30 mW cm^(-2)for Zn-N_(2)batteries.This discovery implements another avenue for the exploration of Zn-N_(2)battery materials and holds broader significance for advancing the field of energy storage and conversion.展开更多
基金supported by Project of Combination of Producing,Learning and Studying of Guangdong Province and Education Department(2011B090400027)
文摘Ba0.85Ca0.15Ti0.9Zr0.1O3 （BCTZ） lead-free piezoelectric ceramics co-doped with CeO2 （x=0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%） and Li2CO3 （0.6 wt.%） were prepared by conventional solid-state reaction method. Influence of CeO2 doping amount on the piezoelectric properties, dielectric properties, phase composition and microstructure of prepared BCTZ lead-free piezoelectric ceramics doped with Li2CO3 were investigated by X-ray diffraction （XRD） and scanning electron microscopy （SEM） and other analytical methods. The results showed that the sintered temperature of BCTZ lead-free piezoelectric ceramics doped with CeO2 decreased greatly when Li2CO3 doping amount was 0.6 wt.%;a pure perovskite structure of BCTZ lead-free piezoelectric ceramics co-doped with Li2CO3 and CeO2 and sintered at 1050 ℃ could also be obtained. The piezoelectric constant （d33）, the relative permit-tivity （εr） and the planar electromechanical coupling factor （kp） of BCTZ ceramics doped with Li2CO3 increased firstly and then de-creased, the dielectric loss （tanδ） decreased firstly and then increased and decreased at last when CeO2 doping amount increased. The influence of CeO2 doping on the properties of BCTZ lead-free piezoelectric ceramics doped with Li2CO3 were caused by“soft effect”and “hard effect”piezoelectric additive and causing lattice distortion. When CeO2 doping amount （x） was 0.2 wt.%, the BCTZ ceramics doped with Li2CO3 （0.6 wt.%） and sintered at 1050 ℃ possessed the best piezoelectric property and dielectric property with d33 of 436 pC/N, kp of 48.3%,εr of 3650, tanδof 1.5%.
文摘Quinary system piezoelectric ceramics PSN-PZN-PMS-PZT were prepared by using a two-step method. The effects of CeO2 doping on piezoelectric and dielectric properties of the system were investigated at morphotropic phase boundary （MPB）. The results reveal that the relative dielectric constant ε33^T｜ε0, the Curie temperature To, the piezoelectric constant d33, the mechanical quality factor Qm, and the electromechanical coupling coefficient Kp are changed with the increase of CeO2 content. On the other hand, the effects of CeO2 doping on the dielectric properties of PSN-PZN-PMS-PZT piezoelectric ceramics at high electric field are consistent with the change at weak electric field. The values of dielectric constant and dielectric loss are enhanced with the increasing of electric field.
基金financially supported by the National Natural Science Foundation of China(No.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.
基金financial support from 2024 Domestic Visiting Scholar Program for Teachers'Professional Development in Universities(Grant No.FX2024022)National Natural Science Foundation of China(Grant No.61904043)。
文摘The development of optoelectronic technologies demands photodetectors with miniaturization,broadband operation,high sensitivity,and low power consumption.Although 2D van der Waals(vd W)heterostructures are promising candidates due to their built-in electric fields,ultrafast photocarrier separation,and tunable bandgaps,defect states limit their performance.Therefore,the modulation of the optoelectronic properties in such heterostructures is imperative.Surface charge transfer doping(SCTD)has emerged as a promising strategy for non-destructive modulation of electronic and optoelectronic characteristics in two-dimensional materials.In this work,we demonstrate the construction of high-performance p-i-n vertical heterojunction photodetectors through SCTD of MoTe_(2)/ReS_(2)heterostructure using p-type F_(4)-TCNQ.Systematic characterization reveals that the interfacial doping process effectively amplifies the built-in electric field,enhancing photogenerated carrier separation efficiency.Compared to the pristine heterojunction device,the doped photodetector exhibits remarkable visible to nearinfrared(635-1064 nm)performance.Particularly under 1064 nm illumination at zero bias,the device achieves a responsivity of 2.86 A/W and specific detectivity of 1.41×10^(12)Jones.Notably,the external quantum efficiency reaches an exceptional value of 334%compared to the initial 11.5%,while maintaining ultrafast response characteristics with rise/fall times of 11.6/15.6μs.This work provides new insights into interface engineering through molecular doping for developing high-performance vd W optoelectronic devices.
基金supported by National Natural Science Foundation of China (21876168, 21507130)Youth Innovation Promotion Association of CAS (2019376)the Chongqing Science & Technology Commission (cstc2016jcyjA0070, cstckjcxljrc13)~~
文摘Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods were used as supports to prepare MnOx/CeO2‐NR, MnOx/CZ‐NR, MnOx/CA‐NR, and MnOx/CS‐NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high‐resolution TEM, X‐ray diffraction, Raman and N2‐physisorption analyses, hydrogen temperature‐programmed reduction, ammonia temperature‐programmed desorption, in situ diffuse reflectance infrared Fourier‐transform spectroscopic analysis of the NH3 adsorption, and X‐ray photoelectron spectroscopy. Moreover, the catalytic performance and H2O+SO2 tolerance of these samples were evaluated through NH3‐selective catalytic reduction (NH3‐SCR) in the absence or presence of H2O and SO2. The obtained results show that the MnOx/CS‐NR catalyst exhibits the highest NOx conversion and the lowest N2O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn4+ content, and the lowest redox ability. The MnOx/CS‐NR catalyst also presents excellent resistance to H2O and SO2. All of these phenomena suggest that Si4+ is the optimal dopant for the MnOx/CeO2‐NR catalyst.
基金the National Basic Research Program of China (973 program, No. 2004 CB 7195040)
文摘Doping of different rare-earth metals （Pr, Nd, Y and La） had an evident influence on the catalytic performance of CuO-CeO2 for the preferential oxidation （PROX） of CO in excess hydrogen. As for Pr, the doping enhanced the catalytic activity of CuO-CeO2 for PROX. For example, the CO conversion over the above catalyst for PROX was higher than 99% at 120 °C. Especially, the doping of Pr widened the temperature window by 20 °C over CuO-CeO2 with 99% CO conversion. For Nd, Y, and La, the doping depressed the catalytic activity of CuO-CeO2 for PROX. However, the doping of transition metals markedly improved the selectivity of CuO-CeO2 for PROX.
基金supported by the National Natural Science Foundation of China(Nos.52172243,52371215)。
文摘All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.
文摘To improve the oxidation resistance of HfB_(2)-SiC coatings on carbon/carbon composites at 1700°C in air,CeO_(2) was introduced to improve oxygen blocking and its mechanism was investigated.During the rapid oxidation stage,CeO_(2) accelerated the formation of a multiphase glass layer on the coating surface.The maximum oxidation rates of CeO_(2)-HfB2-SiC coatings with 1%,3%,and 5%CeO_(2) were 24.1%,20.3%,and 53.2%higher than that of the unmodified HfB2-SiC coating,respectively.In the stable oxidation stage,the maximum oxidation rates of coatings with 1%and 3%CeO_(2) decreased by 31.4%and 21.9%,respectively,demonstrating adequate inert protection.CeO_(2) is a“coagulant”and“stabilizer”in the composite glass layer.However,increasing the CeO_(2) content accelerates the reaction between the SiO_(2) glass phase and SiC,leading to a higher SiO_(2) consumption and reduced self-healing ability of the glass layer.The 1%CeO_(2)-60%HfB2-39%SiC coating showed improved glass layer viscosity and stability,moderate SiO_(2) consumption,and better self-healing ability,significantly boosting the oxidation protection of the coating.
基金supported by the National Natural Science Foundation of China(No.52122407,No.52174285,52404317)the Science and Technology Innovation Program of Hunan Province(No.2022RC3048).
文摘LiNiO_(2)(LNO)is one of the most promising cathode materials for lithium-ion batteries.Tungsten element in enhancing the stability of LNO has been researched extensively.However,the understanding of the specific doping process and existing form of W are still not perfect.This study proposes a lithium-induced grain boundary phase W doping mechanism.The results demonstrate that the introduced W atomsfirst react with the lithium source to generate a Li–W–O phase at the grain boundary of primary particles.With the increase of lithium ratio,W atoms gradually diffuse from the grain boundary phase to the interior layered structure to achieve W doping.The feasibility of grain boundary phase doping is verified byfirst principles calculation.Furthermore,it is found that the Li2WO4 grain boundary phase is an excellent lithium ion conductor,which can protect the cathode surface and improve the rate performance.The doped W can alleviate the harmful H2↔H3 phase transition,thereby inhibiting the generation of microcracks,and improving the electrochemical performance.Consequently,the 0.3 wt%W-doped sample provides a significant improved capacity retention of 88.5%compared with the pristine LNO(80.7%)after 100 cycles at 2.8–4.3 V under 1C.
文摘Cerium oxide is an earth-abundant,highly researched multifunctional oxide with great technological importance and wide applications area.Trivalent rare earth(RE^(3+))dopants modify the defects concentration,create plenty of Ce^(3+)■Ce^(4+)redox centres and generate numerous oxygen vacancies than the pure ceria.In the present work,CeO_(2)(CE),10 mol%Gd doped ceria(Ce_(0.9)Gd_(0.1)O_(2-δ);CGO),and 10 mol%Sm doped ceria(Ce_(0.9)Sm_(0.1)O_(2-δ);CSO)were synthesized by sol-gel auto-combustion method.The phase formation,particle morphology,and elemental distribution of the synthesized powder samples were studied by X-ray diffraction,Fourier transform infrared spectroscopy,field emission scanning electron microscopy,and energy dispersive X-ray analysis.UV-diffuse reflectance spectroscopy was used to study the optical properties of the material.The band gaps of the CE,CSO and CGO were calculated to be2.81,2.71 and 2.60 eV,respectively.Electrochemical impedance spectroscopy(EIS)at room temperature(RT)investigated the materials'electrical properties.The improved electrical conductivity was registered for the doped variants.CGO reaches the highest one(0.4×10^(-7)S/cm)at RT.Cyclic voltammetry(CV)was performed to study the oxidation-reduction behavior and reversibility of the ion intercalation-deintercalation process of the materials in an electrolyte solution.For the doped ceria,a threefold improved current density is observed for the cathodic part,while a small improvement is reflected in the anodic part.Specific capacitance(C_(sp))was calculated at the Faradaic and non-Faradaic region of the voltammograms.C_(sp)of the materials increases in the order of CE<<CSO<CGO.The highest Csp 345.16 F/g at a scan rate of 5 mV/s is obtained for the CGO.Lastly,a correlation is drawn by analysing cyclic voltammograms to conclude the applicability of the doped ceria material for roomtemperature water-electrolysis in the alkaline medium.
基金supported by National Natural Science Foundation of China (52204376)Youth Foundation of Hebei Province (E2022103007)+1 种基金Open Project of Yunnan Precious Metals Laboratory Co.(YPML-20240502059)Young Elite Scientists Sponsorship Program by CAST (2021QNRC001)。
文摘There has been a continuous effort to improve the thermal stability of subnanometric platinum(Pt)cluster(<2 nm) catalyst because Pt cluster on CeO_(2) support can be mobile and aggregated into nanoparticle on heating at elevated temperatures,yet this great challenge remains.In this study,a strategy is reported to improve the thermal stability of subnanometric Pt cluster by hydrothermal deposition method.Based on this method,zirconium(Zr) was precisely doped on surface of Ce_(0.95)Zr_(0.05)O_(2) by accurately controlling Pt subnanometric cluster size.The surface doping of Zr is favorable for forming the Zr-O-Ce site and activating surface lattice oxygen atoms,which results in strong electronic interactions to stabilize the Pt subnanometric cluster.After high-temperature aging treatment at 1000℃/4 h,the single atom Pt supported on CeO_(2) is aggregated into larger sized(>3 nm) nanoparticle.In contrast,the single atom Pt supported on Ce_(0.95)Zr_(0.0)5O_(2) displays less agglomeration into subnanometric cluster with size of(1.4±0.3) nm.Moreover,the CO oxide catalytic performance of Ce_(0.95)Zr_(0.0)5O_(2)-Pt is 26% and 31%higher than that of CeO_(2)-Pt and commercial Al_(2)O_(3)-Pt catalysts,respectively.The experimental and density functional theory(DFT) calculations indicate that the Zr-O-Ce site and Pt subnanometric cluster interface have more defect sites and active oxygen species than CeO_(2)-Pt interface,which activate the Mars van Krevelen(MvK) mechanism,facilitating the catalytic performance.
基金the support of the Henry Royce Institute for Advanced Materials through the Industrial Collaboration Programme(RICP-R4-100061)and MATcelerateZero(MATZ0)funded from a grant provided by the Engineering and Physical Sciences Research Council EP/X527257/1+6 种基金the Department for Energy Security and Net Zero(Project ID:NEXTCCUS)University College London’s Research,Innovation and Global Engagement,University of Sydney–University College London Partnership Collaboration AwardsUCL-Peking University Strategic Partner FundsCornell-UCL Global Strategic Collaboration Awards and IISc-UCL Joint seed fund for their financial supportthe ACT program(Accelerating CCS Technologies,Horizon2020 Project No.691712)for the financial support of the NEXTCCUS project(project ID:327327)Cambridge Royce facilities grant EP/P024947/1Sir Henry Royce Institute–recurrent grant EP/R00661X/1。
文摘Integrating electrocatalytic and photocatalytic functionalities into a single-component system offers a promising strategy for enhancing catalytic activity in photo-assisted electrocatalysis.This synergy is critical for advancing energy conversion efficiency,yet significant challenges persist,particularly in optimizing individual layers and minimizing charge recombination.In this work,we present a novel singlecomponent photo-assisted electrocatalytic system based on Ni-or Co-doped CeO_(2),which simultaneously functions as a light absorber and electrocatalyst.We elucidate the critical relationship between bandgap engineering and d-band states,demonstrating that controlled modulation of dopant-derived 3d states within the CeO_(2)bandgap facilitates visible-light harvesting and optimizes the adsorption energetics of key reaction intermediates.Specifically,Ni-doped CeO_(2)introduces additional 3d states near the Fermi level,narrowing the bandgap from 3.0 to 2.7 eV.This modification not only enhances visible-light absorption but also improves charge transfer efficiency at the catalyst-electrolyte interface.Density functional theory(DFT)calculations and spectroscopic analyses reveal that Ni doping significantly enhances performance,achieving a 64 mV reduction in overpotential at 50 mA/cm^(2)under illumination,while Co-doped CeO_(2)exhibits a 35 mV reduction in 1 M NaOH.Our findings demonstrate that a simple doping strategy can tailor 3d states to promote efficient charge carrier separation and intermediate transfer,offering a versatile and scalable approach to designing advanced electrocatalysts for water splitting.
基金Project supported by the Natural Science Foundation of Sichuan Province(2024NSFSC0219)。
文摘In this work,the rare-earth doped ternary lead zirconate titanate ceramics with chemical formula of[0.3 Pb(Zn_(1/3)Nb_(2/3))O_(3)-0.7Pb(Zr_(0.52)Ti_(0.48))O_(3)]+x wt%CeO_(2)(x=0-0.5,abbreviated as 0.3PZN-0.7PZT-xCe)were synthesized by a conventional solid-state reaction route,specific attentions was focused on the effects of CeO_(2)dopants on the structures and electrical properties of the 0.3PZN-0.7PZT ceramics,revealing the role conve rsion of CeO_(2)dopants with its doping amount(x).When less CeO_(2)(x≤0.2)is introduced into 0.3PZN-0.7PZT,the prepared ceramics are identified as the coexistence of rhombohedral and tetragonal phases,also involved with an increased grain size and a reduced atomic ratio of Pb/(Zr+Ti+Zn+Nb).The increased remanent polarization(Pr)and deceased coercive filed(Ec),as well as improved dielectric permittivity(er)and piezoelectric coefficient(d_(33))de monstrate the donor substitution of Ce^(3+)for Pb^(2+)at the A-site of perovskite lattice.Conversely,the introduction of excessive CeO_(2)(x>0.2)causes a reversal evolution in the electrical properties of ceramics,suggesting that some of the introduced cerium element tends to become Ce4+,which equivalently substitutes for Zr^(4+)at the B-site.Additionally,the diffused phase transition(DPT)behaviors of the 0.3PZN-0.7PZT-xCe ceramics were investigated by the modified Curie-Weiss Law.The sample with x=0.2 shows reduced DPT character and optimized electrical properties,including TC=297℃,εr=1400,d_(33)=480 pC/N,tanδ=1.6%,kp=65%,d_(33)·g_(33)=16.32×10^(-12)m^(2)/N,Pr=38.3μC/cm^(2)and Ec=1.02 kV/mm.These enhanced electrical properties not only are contributed by the donor substitution effect of Ce^(3+),but also benefit from the optimized morphotropic phase boundary that is close to the tetragonal-rich side.
基金National Natural Science Foundation of China(21968020,22302222)Natural Science Foundation of Inner Mongolia(2022MS02011)+3 种基金China Postdoctoral Science Foundation under Grant Number(2024T170965,2023M743641)Science and Technology Projects of China Northern Rare Earth(BFXT-2022-D-0023)Science and Technology Department of Shanxi Province(202303021222409)Education Department of Inner Mongolia Autonomous Region(NJZZ23094,NJYT23039)。
文摘Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based catalysts.Herein,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO_(2)nanorods were effectively created,with adjustable vacancy/Cu ratio.The resulting optimum catalyst shows up to 79%catalytic current density to hydrocarbons(excluding CO),with 49%faradaic efficiency to CH4.Experiments and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to hydrocarbons.These findings may spur new insights for designing and developing more controllable chemical process relevant to CO_(2)utilization.
基金supported by the Natural Science Foundation of Henan Province,China(No.242300421226)the scientific research program of innovation platform in State Tobacco Monopoly Administration.
文摘Nitrogen dioxide(NO_(2))is a significant air pollutant with harmful effects on human health and the environment.Timely and accurate monitoring of NO_(2)concentrations is crucial for improving air quality and protecting public health.However,quantifying NO_(2)in the presence of other gases remains challenging.Herein,we integrate Ru onto the MoS_(2)surface to form Ru-S-Mo active sites,thereby tuning the electronic structure of MoS_(2)for enhanced NO_(2)detection.This sensor shows excellent sensitivity(29.7%at 100×10^(-6)NO_(2)and 25℃),with a linear response to NO_(2)ranging from 0.5 to 200×10^(-6),and a significantly reduced response/recovery time from 160/3636 s for pure MoS_(2)to 58/427 s for Ru@MoS_(2)at 100×10^(-6)NO_(2).Additionally,the sensor is highly selective for NO_(2),exhibiting a response 14 times higher than for other gases,and possesses strong anti-interference capabilities,accurately quantifying NO_(2)in the presence of varying H_(2)concentrations(10×10^(-6)-200×10^(-6))with a low RSD of 5.34%.A portable wireless NO_(2)monitoring system was successfully constructed using Ru@MoS_(2),enabling real-time gas leak detection(10×10^(-6)-50×10^(-6))with hazard warnings and maintaining a stable response to NO_(2)over a 4-week period.This work extends the gas sensing applications of MoS_(2)and provides a portable,wireless,and high-selectivity NO_(2)sensing method for environmental monitoring and safety assurance.
基金supported by the Postdoctoral Fellowship Program of CPSF(No.GZC20231545)the China Postdoctoral Science Foundation(Nos.2024T170557 and 2023M742224)+6 种基金the Shanghai Post-doctoral Excellence Program(No.2023440)the National Natural Science Foundation of China(Nos.52127801,52401101,and 22205012)the Shenzhen Basic Research Project(Nos.JCYJ20210324120001003,JCYJ20200109144608205)the Guangdong Basic and Applied Basic Research Foundation(Nos.2020A1515011301 and 2021A1515012246)the IER Foundation(Nos.IERF202201 andIERF202202),the City University of Hong Kong Donation Research(No.DON-RMG 9229021)the Hong Kong PDFS-RGC Postdoctoral Fellowship Scheme(Nos.PDFS2122–1S08 and CityU 9061014)the Hong Kong HMRF(Health and Medical Research Fund)(Nos.2120972 and CityU 9211320).
文摘The poor corrosion resistance of magnesium(Mg)and its alloys limits their application in various fields.Micro arc oxidation(MAO)coatings can improve the corrosion resistance,but the pore defects and low surface hardness make them susceptible to wear and accelerated corrosion during usage.In this study,a ZrO_(2)nanoparticles doped-MAO coating is prepared on the ZK61 Mg alloy by utilizing an MgF_(2)passivation layer to prevent ablation.The ZrO_(2)nanoparticles re-melt and precipitate due to local discharging,which produces evenly dispersed nanocrystals in the MAO coating.As a result,the hardness of the MAO coating with the appropriate ZrO_(2)concentration increases by over 10 times,while the wear rate decreases and corrosion resistance increases.With increasing ZrO_(2)concentrations,the corrosion potentials increase from−1.528 V of the bare ZK61 Mg alloy to−1.184 V,the corrosion current density decreases from 1.065×10^(–4)A cm^(–2)to 3.960×10^(–8)A cm^(–2),and the charge transfer resistance increases from 3.41×10^(2)Ωcm^(2)to 6.782×10^(5)Ωcm^(2).Immersion tests conducted in a salt solution for 28 d reveal minimal corrosion in contrast to severe corrosion on the untreated ZK61 Mg alloy.ZrO_(2)nanoparticles improve the corrosion resistance of MAO coatings by sealing pores and secondary strengthening of the corrosion product layer.
基金supported by the National Natural Science Foundation of China(51974167)Natural Science Foundation Youth Foundation of Inner Mongolia(2023QN05038)Higher Education Carbon Peak Carbon Neutral Research Project of Inner Mongolia Autonomous Region(STZX202210)。
文摘PrBaFe_(2)O_(5+δ)(PBF)is one of the promising cathode materials for intermediate-temperature solid oxide fuel cell(IT-SOFC)technology.However,as the operating temperature decreases,the electrochemical performance of this material deteriorates rapidly.To counter this,various doping strategies have been tested and reported in order to improve the electrochemical properties of this material at intermediate-temperatures.In this study,Mg-doping to partially substitute Fe of PBF was investigated.PrBaFe_(2-x)Mg_(x)O_(5+δ)(PBFMgx,x=0.1,0.15,0.2,0.3)materials were successfully synthesized,and their electrochemical performance as IT-SOFC cathode was evaluated.It is shown that Mg-doping enhances the conductivity of PBF between 650 and 800℃,impacts little on the area-specific resistance of oxygen reduction reaction at and above 700℃,and,most significantly,improves the power density of the NiSDC/SDC/PBFMg0.15single cell by 52%compared to the un-doped PBF.This enhanced electrochemical performance is attributed to the improvement in PBF conductivity by Mg-doping.
基金financially supported by the National Natural Science Foundation of China (No.52071146)Guangdong Provincial Natural Science Foundation (No.2023A1515010989)the Science and Technology Projects in Guangzhou (No.202201000008)。
文摘Water purification systems based on transition metal dichalcogenides face significant challenges,including lack of reactivity under dark conditions,scarcity of catalytically active sites,and rapid recombination of photogenerated charge carriers.Simultaneously increasing the number of active sites and improving charge separation efficiency has proven difficult.In this study,we present a novel approach combining molybdenum(Mo) monoatomic doping and size engineering to produce a series of Mo-ReS_(2) quantum dots(MR QDs) with controllable dimensions.High-resolution structural characterization,first-principle calculations,and piezo force microscopy reveal that Mo monoatomic doping enhances the lattice asymmetry,thereby improving the piezoelectric properties.The resulting piezoelectric polarization and the generated built-in electric field significantly improve charge separation efficiency,leading to optimized photocatalytic performance.Additionally,the doping strategy increases the number of active sites and improves the adsorption of intermediate radicals,substantially boosting photo-sterilization efficiency.Our results demonstrate the elimination of 99.95% of Escherichia coli and 100.00% of Staphylococcus aureus within 30 min.Furthermore,we developed a self-purification system simulating water drainage,utilizing low-frequency water streams to trigger the piezoelectric behavior of MR QDs,achieving piezoelectric synergistic photodegradation.This innovative approach provides a more environmentally friendly and economical method for water self-purification,paving the way for advanced water treatment technologies.
基金funded by the Natural Science Foundation of China (No. 21603109)the Henan Joint Fund of the National Natural Science Foundation of China (No. U1404216)+1 种基金the Scientific Research Program Funded by Shaanxi Provincial Education Department (No. 20JK0676)supported by Natural Science Basic Research Program of Shanxi (Nos. 2022JQ-108, 2022JQ096)。
文摘Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),CrS_(2)with one S vacancy(v-CrS_(2)), and Ti doped CrS_(2)(Ti@CrS_(2)). The results have shown that the pristine CrS_(2)exhibits inert character for NO activation. However, v-CrS_(2)and Ti@CrS_(2)can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates(0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts(-0.96~-1.64 e V), compared to the situation of CrS_(2)(0.065 e/-0.30 e V). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS_(2)and Ti@CrS_(2)all exhibit ultralow limiting potentials of-0.03~-0.47 V, following both*NOH and*NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.
基金supported by the Special Project for Local Science and Technology Development Guided by the Central Government of China(No.236Z1406G)。
文摘Zn-N_(2)batteries,which are comprised of nitrogen reduction reaction(NRR)and oxygen evolution reaction(OER),represent an emerging technology for efficient ammonia production and simultaneous power generation.Nevertheless,the intrinsic limitations of NRR and OER currently preclude its advancement.In this paper,Co and B co-doped Lavoisier framework series materials(MIL)are synthesized.Rapid mass transfer is rendered feasible with B_(0.25)-MIL-88-Fe_(4)Co_(1) by the distinctive double cone microrods structure.The addition of soft acid metal node Co^(2+)and B with defective electronic structure modifies the electronic configuration of MIL-88-Fe.At the same time,doping causes defects in the metal-organic frameworks,expands effectively the pore size,and increases the specific surface area,thereby expediting the adsorption of N_(2)and the release of O_(2).The electrocatalysis results show that the dual-doping scheme increases the NH_(3)yield(127.27μg^(-1)h^(-1)mg_(cat)^(-1))and Faraday efficiency(25.81%)while reducing the overpotential of OER(330 mV),achieving a power density of 8.30 mW cm^(-2)for Zn-N_(2)batteries.This discovery implements another avenue for the exploration of Zn-N_(2)battery materials and holds broader significance for advancing the field of energy storage and conversion.
