Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO_(2)reduction and aryl alcohol oxidation

Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.

Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO_(2) reduction

The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.

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

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

Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO_(2) electroreduction

Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.

Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO_(2) electroreduction to CH_(4)

Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.

Single-atom modified graphene cocatalyst for enhanced photocatalytic CO_(2) reduction on halide perovskite

Metal halide perovskite(MHP)has become one of the most promising materials for photocatalytic CO_(2) reduction owing to the wide light absorption range,negative conduction band position and high reduction ability.However,photoreduction of CO_(2) by MHP remains a challenge because of the slow charge separation and transfer.Herein,a cobalt single-atom modified nitrogen-doped graphene(Co-NG)cocatalyst is prepared for enhanced photocatalytic CO_(2) reduction of bismuth-based MHP Cs_(3)Bi_(2)Br_(9).The optimal Cs_(3)Bi_(2)Br_(9)/Co-NG composite exhibits the CO production rate of 123.16μmol g^(-1)h^(-1),which is 17.3 times higher than that of Cs_(3)Bi_(2)Br_(9).Moreover,the Cs_(3)Bi_(2)Br_(9)/Co-NG composite photocatalyst exhibits nearly 100% CO selectivity as well as impressive long-term stability.Charge carrier dynamic characterizations such as Kelvin probe force microscopy(KPFM),single-particle PL microscope and transient absorption(TA)spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance.The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement.In addition,in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers,demonstrating that the introduction of Co-NG promotes the formation of ^(*)COOH intermediate,providing sufficient evidence for the highly selective generation of CO.This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO_(2) reduction and is expected to shed light on other photocatalytic applications.

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.

Synergistic effect of heterogeneous single atoms and clusters for improved catalytic performance

Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer process,which limits the efficiency of electrocatalytic water splitting.Therefore,it is urgent to develop highly active OER catalysts to accelerate reaction kinetics.Coupling single atoms and clusters in one system is an innovative approach for developing efficient catalysts that can synergistically optimize the adsorption and configuration of intermediates and improve catalytic activity.However,research in this area is still scarce.Herein,we constructed a heterogeneous single-atom cluster system by anchoring Ir single atoms and Co clusters on the surface of Ni(OH)_(2)nanosheets.Ir single atoms and Co clusters synergistically improved the catalytic activity toward the OER.Specifically,Co_(n)Ir_(1)/Ni(OH)_(2)required an overpotential of 255 mV at a current density of 10 mA·cm^(−2),which was 60 mV and 67 mV lower than those of Co_(n)/Ni(OH)_(2)and Ir1/Ni(OH)_(2),respectively.The turnover frequency of Co_(n)Ir_(1)/Ni(OH)_(2)was 0.49 s^(−1),which was 4.9 times greater than that of Co_(n)/Ni(OH)_(2)at an overpotential of 300 mV.

Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting

The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction(OER).However,improving the overall water splitting performance remains a challenging task.By building metal organic framework(MOF)on MOF heterostructures,an efficient strategy for controlling the electrical structure of MOFs was presented in this study.ZIF-67 was in-situ synthesized on MIL-88(Fe)using a two-step self-assembly method,followed by low-temperature phosphorization to ultimately synthesize FeP-CoP_(3)bimetallic phosphides.By combining atomic orbital theory and theoretical calculations(density functional theory),the results reveal the successful modulation of electronic orbitals in FeP-CoP_(3)bimetallic phosphides,which are synthesized from MOF on MOF structure.The synergistic impact of the metal center Co species and the phase conjugation of both kinds of MOFs are responsible for this regulatory phenomenon.Therefore,the catalyst demonstrates excellent properties,demonstrating HER 81 mV(η10)in a 1.0 mol L^(−1)KOH solution and OER 239 mV(η50)low overpotentials.The FeP-CoP_(3)linked dual electrode alkaline batteries,which are bifunctional electrocatalysts,have a good electrocatalytic ability and may last for 50 h.They require just 1.49 V(η50)for total water breakdown.Through this technique,the electrical structure of electrocatalysts may be altered to increase catalytic activity.

Single-atom catalysts based on polarization switching of ferroelectric In_(2)Se_(3) for N_(2) reduction

The polarization switching plays a crucial role in controlling the final products in the catalytic pro-cess.The effect of polarization orientation on nitrogen reduction was investigated by anchoring transition metal atoms to form active centers on ferroelectric material In_(2)Se_(3).During the polariza-tion switching process,the difference in surface electrostatic potential leads to a redistribution of electronic states.This affects the interaction strength between the adsorbed small molecules and the catalyst substrate,thereby altering the reaction barrier.In addition,the surface states must be considered to prevent the adsorption of other small molecules(such as *O,*OH,and *H).Further-more,the V@↓-In_(2)Se_(3) possesses excellent catalytic properties,high electrochemical and thermody-namic stability,which facilitates the catalytic process.Machine learning also helps us further ex-plore the underlying mechanisms.The systematic investigation provides novel insights into the design and application of two-dimensional switchable ferroelectric catalysts for various chemical processes.

Micro-galvanic corrosion behaviour of Mg-(7,9)Al-1Fe-xNd alloys

The localized micro-galvanic corrosion process and the kinetic information of Mg-(7,9)Al-1Fe-x Nd alloys were investigated by in situ observation under electrochemical control and in situ atomic force microscopy(AFM)in an electrolyte environment.The results revealed that the formation of the Nd-rich phase in alloys resulted in a decrease in the Volta potential difference from~400 m V(AlFe3/α-Mg)to~220 mV(Nd-rich/α-Mg),reducing the corrosion products around the cathodic phase and corrosion current density of the microscale area.The addition of Nd significantly improved the corrosion resistance,mainly due to the suppression of the micro-galvanic corrosion between the second phases and substrate.Finally,the corrosion mechanism of Mg-(7,9)Al-1Fe-x Nd alloys was discussed based on in situ observations and electrochemical results.

Cation effects in electrocatalytic reduction reactions:Recent advances

Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.

First‑principles study on electronic structure,optical and magnetic properties of rare earth elements X(X=Sc,Y,La,Ce,Eu)doped with two‑dimensional GaSe

The electronic structure,magnetic,and optical properties of two-dimensional(2D)GaSe doped with rare earth elements X(X=Sc,Y,La,Ce,Eu)were calculated using the first-principles plane wave method based on den-sity functional theory.The results show that intrinsic 2D GaSe is a p-type nonmagnetic semiconductor with an indi-rect bandgap of 2.6611 eV.The spin-up and spin-down channels of Sc-,Y-,and La-doped 2D GaSe are symmetric,they are non-magnetic semiconductors.The magnetic moments of Ce-and Eu-doped 2D GaSe are 0.908μ_(B)and 7.163μ_(B),which are magnetic semiconductors.Impurity energy levels appear in both spin-up and spin-down chan-nels of Eu-doped 2D GaSe,which enhances the probability of electron transition.Compared with intrinsic 2D GaSe,the static dielectric constant of the doped 2D GaSe increases,and the polarization ability is strengthened.The ab-sorption spectrum of the doped 2D GaSe shifts in the low-energy direction,and the red-shift phenomenon occurs,which extends the absorption spectral range.The optical reflection coefficient of the doped 2D GaSe is improved in the low energy region,and the improvement of Eu-doped 2D GaSe is the most obvious.

Observation and characterization of asphalt microstructure by atomic force microscopy

The microstructure of asphalt is investigated by atomic force microscopy （AFM）. In order to analyze the impacts of asphalt types on microstructures, two neat asphalts with different penetration grades （50# and 70#） and one styrene-butadiene-styrene （SBS） modified asphalt are chosen. The influence of short-term aging is also studied. Based on the knowledge of asphalt＇s microproperties, the relationship between microstructures and healing property is analyzed. The results indicate that the microstructures of three asphalts are quite different and the effects of aging on the surface characteristics for different asphalts are also different. It is proposed that the bee structure is a type of wax crystal and it has a close relationship with the ＂bridge-healing＂ mechanism. The findings may reveal the formation mechanism of microstructure and the healing property for asphalts.

Single atom gold catalysts for low-temperature CO oxidation

Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The active sites are traditionally believed to be Au nanoclusters or nanoparticles in the size range of 0.5–5 nm. Only in the last few years have single‐atom Au catalysts been proved to be active for CO oxidation. Recent advances in both experimental and theoretical studies on single‐atom Au catalysts unambiguously demonstrated that when dispersed on suitable oxide supports the Au single atoms can be extremely active for CO oxidation. In this mini‐review, recent advances in the development of Au single‐atom catalysts are discussed, with the aim of illus‐trating their unique catalytic features during CO oxidation.

Formation condition of solid solution type high-entropy alloy

Formation condition of high-entropy alloys with solid solution structure was investigated. Seventeen kinds of the high-entropy alloys with different components were prepared, the influencing factors （the comprehensive atomic radius difference δ, the mixing enthalpy AH and the mixing entropy AS） of phase composition of the alloys were calculated, and the microstructure and phase compositions of alloys were analyzed by using SEM and XRD. The result shows that only the systems with δ≤2.77 and △H≥-8.8 kJ/mol will form high entropy alloy with simple solid solution. Otherwise, intermetallic compounds will exist in the alloys. So, selection of the type of element has important effects on microstructure and properties of high entropy alloys.

Determination of Arsenic and Mercury in Soil by Microwave Digestion and Hidride GenerationAtomic Fluorescence Spectrometry

[Objective] The aim was to develop a rapid, simple method for determina- tion of arsenic and mercury in soil samples by atomic fluorescence spectrometry. [Method] The method for determination of As and Hg in soil by combined atomic fluorescence spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-80.0μg/L of As and 0-8.0 μg/L of Hg, and the detection limits of As and Hg was 0.036 μg/L and 0.015 μg/L, respectively. The precision for elevenfold determination of As at 40.0 ug/L level and Hg at 4.0μg/L level were 1.1% and 2.2%（RSD）, respectively. Recoveries of 103.0%-106.6% for As and 90.0%-95.0% for Hg were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of As and Hg in soil samples.

Friction heat production and atom diffusion behaviors during Mg-Ti rotating friction welding process

An innovative physical simulation apparatus, including high speed camera, red thermal imaging system, and mechanical quantity sensor, was used to investigate the friction heat generation and atom diffusion behavior during Mg-Ti friction welding process. The results show that the friction coefficient mainly experiences two steady stages. The first steady stage corresponds to the Coulomb friction with material abrasion. The second steady stage corresponds to the stick friction with fully plastic flow. Moreover, the increasing rates of axial displacement, temperature and friction coefficient are obviously enhanced with the increase of rotation speed and axial pressure. It can also be found that the there exists rapid diffusion phenomenon in the Mg-Ti friction welding system. The large deformation activated diffusion coefficient is about 105 higher than that activated by thermal.

Ageing process of pre-precipitation phase in Ni_(0.75)Al_(0.05)Fe_(0.2) alloy based on phase field method

By utilizing phase field method combined with analysis on free energy and interatomic potentials, pre-precipitation phase formation and transformation process of Ni0.75Al0.05Fe0.2 alloy in early precipitation stage during the ageing process under 1 000 K were studied. And free energy, microstructures, compositions and volume fractions of pre-precipitation phase and equilibrium phase were analyzed. The simulation results indicate that nonstoichiometric Llo pre-precipitation phase formed first, and then would gradually transform into L12 equilibrium phase. It is discovered that the phase transformation process was closely related to free energy and interatomic potentials. Additionally, it is revealed that free energy of Llo pre-precipitation phase was higher and interatomic potential was smaller than that of L12 equilibrium phase. Therefore, it is concluded that Llo phase was unstable, and phase transformation would occur to L12 which was more stable.

Determination of Chromium and Zinc in Soil by Microwave Digestion and Flame Atomic Absorption Spectrometry

[Objective] The aim was to develop a rapid, simple method for determination of chromium and zinc in soil samples by flame atomic absorption spectrometry.[Method] The method for determination of Cr and Zn in soil by combined flame atomic absorption spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-0.8 mg/L for Cr and 0-0.8 mg/L for Zn, the detection limits of Cr and Zn was 0.0025 mg/L and 0.002 3 mg/L, respectively. Recoveries of 102.4%-103.2% for Cr and 97.7%-98.3% for Zn were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of Cr and Zn in soil samples.