Enhancing multifunctional photocatalysis with acetate-assisted cesium doping and unlocking the potential of Z-scheme solar water splitting

Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.

Optical and electrical properties of two-dimensional anisotropic materials

Two-dimensional(2D) anisotropic materials, such as B-P, B-As, GeSe, GeAs, ReSe2, KP15 and their hybrid systems, exhibit unique crystal structures and extraordinary anisotropy. This review presents a comprehensive comparison of various 2D anisotropic crystals as well as relevant FETs and photodetectors, especially on their particular anisotropy in optical and electrical properties. First, the structure of typical 2D anisotropic crystal as well as the analysis of structural anisotropy is provided. Then, recent researches on anisotropic Raman spectra are reviewed. Particularly, a brief measurement principle of Raman spectra under three typical polarized measurement configurations is introduced. Finally, recent progress on the electrical and photoelectrical properties of FETs and polarization-sensitive photodetectors based on 2D anisotropic materials is summarized for the comparison between different 2D anisotropic materials. Beyond the high response speed, sensitivity and on/off ratio, these 2D anisotropic crystals exhibit highly conduction ratio and dichroic ratio which can be applied in terms of polarization sensors, polarization spectroscopy imaging, optical radar and remote sensing.

Accurate estimation of Li/Ni mixing degree of lithium nickel oxide cathode materials

Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.

Comparative study of nudged elastic band and molecular dynamics methods for diffusion kinetics in solid-state electrolytes

Considerable efforts are being made to transition current lithium-ion and sodium-ion batteries towards the use of solid-state electrolytes.Computational methods,specifically nudged elastic band(NEB)and molecular dynamics(MD)methods,provide powerful tools for the design of solid-state electrolytes.The MD method is usually the choice for studying the materials involving complex multiple diffusion paths or having disordered structures.However,it relies on simulations at temperatures much higher than working temperature.This paper studies the reliability of the MD method using the system of Na diffusion in MgO as a benchmark.We carefully study the convergence behavior of the MD method and demonstrate that total effective simulation time of 12 ns can converge the calculated diffusion barrier to about 0.01 eV.The calculated diffusion barrier is 0.31 eV from both methods.The diffusion coefficients at room temperature are 4.3×10^(-9) cm^(2)⋅s^(−1) and 2.2×10^(-9) cm^(2)⋅s^(−1),respectively,from the NEB and MD methods.Our results justify the reliability of the MD method,even though high temperature simulations have to be employed to overcome the limitation on simulation time.

The relationship between the high-frequency performance of supercapacitors and the type of doped nitrogen in the carbon electrode

Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.

Experimental study on phase noise of terahertz quantum cascade laser frequency comb and dual-comb sources

Frequency combs with equally spaced frequency lines show great potentials for applications in spectroscopy,imag-ing,communications,and so on.In the terahertz frequency region,the quantum cascade laser(QCL)is an ideal radiation source for frequency comb and dual-comb operation.The systematic evaluation of phase noise characteristics of terahertz QCL frequency comb and dual-comb sources is of great importance for high precision measurements.In this work,we present detailed measurements and analysis of the phase noise characteristics of terahertz QCL frequency comb and dual-comb sources emitting around 4.2 THz with repetition frequencies of~6.2 GHz.The measurement results for the current noise of the direct current(DC)sources(that are used to electrically pump the terahertz QCLs)indicate that at 100 Hz,the current noise for DC-1 and DC-2 is 0.3895 and 0.0982 nA/Hz1/2,respectively.Such levels of current noise can be safely disregarded.The phase noise of radio frequency(RF)generators(that are employed for injection locking and phase locking),intermode beatnotes,and dual-comb signals with and without phase-locked loop(PLL)are all measured and compared.The experimental results show that in the free-running mode,the phase noise of the intermode beatnote signals is always lower than that of the dual-comb sig-nals across all frequencies.Additionally,the phase noise induced by the RF generators is negligible.By employing the phase lock-ing technique,the phase noise of the intermode beatnote and dual-comb signals in the low offset frequency band can be signifi-cantly suppressed.At an offset frequency of 100 Hz,the measured phase noise values of the dual-comb line without and with phase locking are 15.026 and-64.801 dBc/Hz,respectively.

Microstructure and Oxidation Behavior of ZrB_(2)-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration

ZrB_(2)-based ceramics typically necessitate high temperature and pressure for sintering,whereas ZrB_(2)-SiC ceramics can be fabricated at 1500℃using the process of reactive melt infiltration with Si.In comparison to the conventional preparation method,reactive synthesis allows for the more facile production of ultra-high temperature ceramics with fine particle size and homogeneous composition.In this work,ZrSi_(2),B4C,and C were used as raw materials to prepare ZrB_(2)-SiC via combination of tape casting and reactive melt infiltration herein referred to as ZBC ceramics.Control sample of ZrB_(2)-SiC was also prepared using ZrB_(2) and SiC as raw materials through an identical process designated as ZS ceramics.Microscopic analysis of both ceramic groups revealed smaller and more uniformly distributed particles of the ZrB_(2) phase in ZBC ceramics compared to the larger particles in ZS ceramics.Both sets of ceramics underwent cyclic oxidation testing in the air at 1600℃for a cumulative duration of 5 cycles,each cycle lasting 2 h.Analysis of the oxidation behavior showed that both ZBC ceramics and ZS ceramics developed a glassy SiO_(2)-ZrO_(2) oxide layer on their surfaces during the oxidation.This layer severed as a barrier against oxygen.In ZBC ceramics,ZrO_(2) is finely distributed in SiO_(2),whereas in ZS ceramics,larger ZrO_(2) particles coexist with glassy SiO_(2).The surface oxide layer of ZBC ceramics maintains a dense structure because the well-dispersed ZrO_(2) increases the viscosity of glassy SiO_(2),preventing its crystallization during the cooling.Conversely,some SiO_(2) in the oxide layer of ZS ceramics may crystallize and form a eutectic with ZrO_(2),leading to the formation of ZrSiO_(4).This leads to cracking of the oxide layer due to differences in thermal expansion coefficients,weakening its barrier effect.An analysis of the oxidation resistance shows that ZBC ceramics exhibit less increase in oxide layer thickness and mass compared to ZS ceramics,suggesting superior oxidation resistance of ZBC ceramics.

Hot Isostatic Pressing and Characterizations of Eu^(3+)-doped(Gd,Lu)_(2)O_(3) Transparent

(Gd,Lu)_(2)O_(3)∶Eu scintillation ceramics have promising applications in the high-energy X-ray imaging.Eu0.1Gd0.6Lu1.3O3 nano-powders with pure phase were prepared from the precursor calcined at 1050℃for 4 h by the co-precipitation method.Using the synthesized nano-powders as initial material,Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics were fabri-cated by vacuum pre-sintering at different temperatures for 2 h and hot isostatic pressing(HIP)at 1750℃for 3 h in ar-gon.The influence of pre-sintering temperature on the microstructure,optical and luminescence properties was investi-gated.The Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics pre-sintered at 1625℃for 2 h combined with HIP post-treatment show the high-est in-line transmittance of 75.2%at 611 nm.The photoluminescence(PL)and X-ray excited luminescence(XEL)spectra of the Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)transparent ceramics demonstrate a strong red emission peak at 611 nm due to the^(5)D_(0)→^(7)F_(2) transition of Eu^(3+).The PL,PLE and XEL intensities of the HIP post-treated Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics show a trend of first ascending and then descending with the increase of pre-sintering temperature.The thermally stimulated lumines-cence(TSL)curve of the HIP post-treated Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics presents one high peak at 178 K and two peaks with lower intensities at 253 K and 320 K.The peak at 320 K may be related to oxygen vacancies,and the lumines-cence peak at 178 K is related to defects caused by the valence state changes of Eu^(3+)ions.

Growth of two-inch free-standing heteroepitaxial diamond on Ir/YSZ/Si(001)substrates via laser-patterned templates

As an ultra-wide bandgap semiconductor,diamond garners significant interest due to its exceptional physical properties^([1–3]).These superior characteristics make diamonds highly promising for applications in power electronics^([4]),deep-ultraviolet detectors^([5]),high-energy particle detectors^([6]),and quantum devices based on color centers^([7]).

An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis

Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditions(160℃)in a NaOH–H2O system with ammelide and ammeline as the main degradation products.The alkaline solvent had an obvious corrosion effect for MFF,as indicated by scanning electron microscopy(SEM).The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),and ^(13)C nuclear magnetic resonance(NMR).Besides,the MFF degradation products that have the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of melamine urea-formaldehyde resins(MUFs).Moreover,the degradation system demonstrated here showed the high degradation efficiency after reusing for 7 times.The degradation process generated few harmful pollutants and no pre-or post-treatments were required,which proves its feasibility in the safe removal or recovery of waste MFF.

Rate and Cycling Performance of Ti and Cu Dopedβ-NaMnO_(2) as Cathode of Sodium-ion Battery

Sodium-ion batteries are economical and environmentally sustainable energy storage batteries.Among them,β-NaMnO_(2),a promising sodium-ion cathode material,is a manganese-based oxide with a corrugated laminar structure,which has attracted significant attention due to its structural robustness and relatively high specific capacity.However,it has short cycle life and poor rate capability.To address these issues,Ti atoms,known for enhancing structural stability,and Cu atoms,which facilitate desodiation,were doped intoβ-NaMnO_(2) by first-principles calculation and crystal orbital Hamilton population(COHP)analysis.β-NaMn_(0.8)Ti_(0.1)Cu_(0.1)O_(2) exhibits a notable increase in reversible specific capacity and remarkable rate properties.Operating at a current density of 0.2C(1C=219 mA·g^(–1))and within a voltage range of 1.8–4.0 V,the modified material delivers an initial discharge capacity of 132 mAh·g^(–1).After charge/discharge testing at current densities of 0.2C,0.5C,1C,3C,and 0.2C,the material still maintains a capacity of 110 mA h·g^(–1).The doping of Ti atoms slows down the changes in the crystal structure,resulting in only minimal variation in the lattice constant c/a during the desodiation process.Mn and Cu engage in reversible redox reactions at voltages below 3.0 V and around 3.5 V,respectively.The extended plateau observed in the discharge curve below 3.0 V signifies that Mn significantly contributes to the overall battery capacity.This study provides insights into modifyingβ-NaMnO_(2) as a cathode material,offering experimental evidence and theoretical guidance for enhancing battery performance in Na-ion batteries.

PZT photonic materials and devices platform

Ferroelectric materials are increasingly garnering substantial interest due to their potential applications in optical communication,optical computing,and sensing,among others.This surge in attention is largely due to recent advancements in the fabrication of high-quality thin films,the precision of domain engineering,and their strong compatibility with complementary metal–oxide–semiconductor(CMOS)processes.

A review of the preparation process and anode stabilization strategies of Zn microbatteries

As a burgeoning energy storage technology,Zn microbatteries(ZMBs)exhibit expansive potential for applications.This article initially presents a method for fabricating ZMBs utilizing interdigitated electrodes,employing advanced techniques such as 3D printing,screen printing,laser etching,and electrodeposition.These methodologies play a crucial role in mitigating anode-related issues,consequently enhancing battery performance.Subsequently,the challenges encountered by ZMBs anodes,including dendrite formation,corrosion passivation,hydrogen evolution,and Zn cycle exfoliation,are thoroughly examined.Lastly,a comprehensive strategy for stabilizing the anode is delineated,encompassing anode material selection,anode structure construction,interface engineering,and electrolyte optimization.In essence,the preparation and fine-tuning of ZMBs present ongoing challenges.With continued research and development efforts,it is anticipated that ZMBs will attain efficient,stable,and secure performance on the microscale,offering enduring and dependable energy solutions for applications in miniature electronic devices and wearable technology.

MatChat: A large language model and application service platform for materials science

The prediction of chemical synthesis pathways plays a pivotal role in materials science research. Challenges, such as the complexity of synthesis pathways and the lack of comprehensive datasets, currently hinder our ability to predict these chemical processes accurately. However, recent advancements in generative artificial intelligence(GAI), including automated text generation and question–answering systems, coupled with fine-tuning techniques, have facilitated the deployment of large-scale AI models tailored to specific domains. In this study, we harness the power of the LLaMA2-7B model and enhance it through a learning process that incorporates 13878 pieces of structured material knowledge data.This specialized AI model, named Mat Chat, focuses on predicting inorganic material synthesis pathways. Mat Chat exhibits remarkable proficiency in generating and reasoning with knowledge in materials science. Although Mat Chat requires further refinement to meet the diverse material design needs, this research undeniably highlights its impressive reasoning capabilities and innovative potential in materials science. Mat Chat is now accessible online and open for use, with both the model and its application framework available as open source. This study establishes a robust foundation for collaborative innovation in the integration of generative AI in materials science.

Energy Landscape and Phase Competition of CsV_(3)Sb_(5),CsV_(6)Sb_(6)and TbMn_(6)Sn_(6)-Type Kagome Materials

Finding viable Kagome lattices is vital for materializing novel phenomena in quantum materials.In this study,we performed element substitutions on CsV_(3)Sb_(5)with space group P 6/mmm,TbMn_(6)Sn_(6)with space group P 6/mmm,and CsV_(6)Sb_(6)with space group R3m,as the parent compounds.Totally 4158 materials were obtained through element substitutions,and these materials were then calculated via density functional theory in high-throughput mode.Afterwards,48 materials were identified with high thermodynamic stability(E_(hull)<5 meV/atom).Furthermore,we compared the thermodynamic stability of three different phases with the same elemental composition and predicted some competing phases that may arise during material synthesis.Finally,by calculating the electronic structures of these materials,we attempted to identify patterns in the electronic structure variations as the elements change.This study provides guidance for discovering promising AM_(3)X_(5)/AM_(6)X_(6)Kagome materials from a vast phase space.

Optimizing band structure of CoP nanoparticles via rich-defect carbon shell toward bifunctional electrocatalysts for overall water splitting

Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.

Human ACE2-Functionalized Gold“Virus-Trap”Nanostructures for Accurate Capture of SARS-CoV-2 and Single-Virus SERS Detection

The current COVID-19 pandemic urges the extremely sensitive and prompt detection of SARS-CoV-2 virus.Here,we present a Human Angiotensin-converting-enzyme 2(ACE2)-functionalized gold“virus traps”nanostructure as an extremely sensitive SERS biosensor,to selectively capture and rapidly detect S-protein expressed coronavirus,such as the current SARS-CoV-2 in the contaminated water,down to the single-virus level.Such a SERS sensor features extraordinary 106-fold virus enrichment originating from high-affinity of ACE2 with S protein as well as“virus-traps”composed of oblique gold nanoneedles,and 109-fold enhancement of Raman signals originating from multi-component SERS effects.Furthermore,the identification standard of virus signals is established by machine-learning and identification techniques,resulting in an especially low detection limit of 80 copies mL^(−1) for the simulated contaminated water by SARS-CoV-2 virus with complex circumstance as short as 5 min,which is of great significance for achieving real-time monitoring and early warning of coronavirus.Moreover,here-developed method can be used to establish the identification standard for future unknown coronavirus,and immediately enable extremely sensitive and rapid detection of novel virus.

Rapid Isolation and Multiplexed Detection of Exosome Tumor Markers Via Queued Beads Combined with Quantum Dots in a Microarray

Tumor-derived exosomes are actively involved in cancer progression and metastasis and have emerged as a promising marker for cancer diagnosis in liquid biopsy.Because of their nanoscale size,complex biogenesis,and methodological limitations related to exosome isolation and detection,advancements in their analysis remain slow.Microfluidic technology offers a better analytic approach compared with conventional methods.Here,we developed a bead-based microarray for exosome isolation and multiplexed tumor marker detection.Using this method,exosomes are isolated by binding to antibodies on the bead surface,and tumor markers on the exosomes are detected through quantum dot(QD)probes.The beads are then uniformly trapped and queued among micropillars in the chip.This design benefits fluorescence observation by dispersing the signals into every single bead,thereby avoiding optical interference and enabling more accurate test results.We analyzed exosomes in the cell culture supernatant of lung cancer and endothelial cell lines,and different lung cancer markers labeled with three QD probes were used to conduct multiplexed detection of exosome surface protein markers.Lung cancer-derived samples showed much higher(~sixfold-tenfold)fluorescence intensity than endothelial cell samples,and different types of lung cancer samples showed distinctive marker expression levels.Additionally,using the chip to detect clinical plasma samples from cancer patients showed good diagnostic power and revealed a well consistency with conventional tests for serological markers.These results provide insight into a promising method for exosome tumor marker detection and early-stage cancer diagnosis.

Growth and characterization ofβ-Ga_(2)O_(3)thin films grown on off-angled Al_(2)O_(3)substrates by metal-organic chemical vapor deposition

Beta-gallium oxide(β-Ga_(2)O_(3))thin films were deposited on c-plane(0001)sapphire substrates with different mis-cut angles along<>by metal-organic chemical vapor deposition(MOCVD).The structural properties and surface morphology of as-grownβ-Ga_(2)O_(3)thin films were investigated in detail.It was found that by using thin buffer layer and mis-cut substrate technology,the full width at half maximum(FWHM)of the()diffraction peak of theβ-Ga_(2)O_(3)film is decreased from 2°on c-plane(0001)Al_(2)O_(3)substrate to 0.64°on an 8°off-angled c-plane(0001)Al_(2)O_(3)substrate.The surface root-mean-square(RMS)roughness can also be improved greatly and the value is 1.27 nm for 8°off-angled c-plane(0001)Al_(2)O_(3)substrate.Room temper-ature photoluminescence(PL)was observed,which was attributed to the self-trapped excitons formed by oxygen and gallium vacancies in the film.The ultraviolet-blue PL intensity related with oxygen and gallium vacancies is decreased with the increas-ing mis-cut angle,which is in agreement with the improved crystal quality measured by high resolution X-ray diffraction(HR-XRD).The present results provide a route for growing high qualityβ-Ga_(2)O_(3)film on Al_(2)O_(3)substrate.

The application of perovskite materials in solar water splitting

Solar water splitting is a promising strategy for sustainable production of renewable hydrogen,and solving the crisis of energy and environment in the world.However,large-scale application of this method is hampered by the efficiency and the expense of the solar water splitting systems.Searching for non-toxic,low-cost,efficient and stable photocatalysts is an important way for solar water splitting.Due to the simplicity of structure and the flexibility of composition,perovskite based photocatalysts have recently attracted widespread attention for application in solar water splitting.In this review,the recent developments of perovskite based photocatalysts for water splitting are summarized.An introduction including the structures and properties of perovskite materials,and the fundamentals of solar water splitting is first provided.Then,it specifically focuses on the strategies for designing and modulating perovskite materials to improve their photocatalytic performance for solar water splitting.The current challenges and perspectives of perovskite materials in solar water splitting are also reviewed.The aim of this review is to summarize recent findings and developments of perovskite based photocatalysts and provide some useful guidance for the future research on the design and development of highly efficient perovskite based photocatalysts and the relevant systems for water splitting.