材料类专业在专业建设和本科生就业方面的几点思考

我国材料产业的快速发展,对材料类专业建设和人才培养提出了更高的要求。本文结合我校材料科学与工程的专业建设特色,对我国材料类专业的几个常见问题和本科生就业现状进行了分析和总结,为专业改革和人才培养提供参考。

Activating d^(10)electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H_(2)by surface atomic arrangement

Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.

Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H_(2)O_(2) production by using femtosecond transient absorption spectroscopy

Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.

Pitch-derived soft carbon composite with hard carbon fibers for high-rate and long-cycling K^(+) storage

Potassium-ion batteries(KIBs)have been seen as a competitive alternative to lithium-ion batteries(LIBs)due to their natural abundance,low cost and rocking chair-like operating mechanism similar to LIBs.Soft carbon has a lower voltage plateau compared to hard carbon and an easily modulated lattice structure compared to graphite,which provides particular advantages in KIBs anodes.Pitch has attracted much attention as a simple,readily available and inexpensive precursor for soft carbon,but its structure is easily damaged during cycling.Herein,the flexible film Pitch@CNF are prepared by uniformly winding reticulated carbon fibers on the surface of pitch-soft carbon via electrostatic spinning technique,which not only enables the pitch to maintain its structure well during cycling and withstand the volume expansion upon K^(+) insertion,but also is conducive to ionic transport of the three-dimensional reticulated structure.Meanwhile,the abundant pores on the carbon fibers can provide more K^(+) active sites.The prepared flexible self-supporting films can be used directly as electrodes without the addition of binders and conductive agents.The reversible capacity is 290 mAh·g^(-1)at a current density of 0.1 A·g^(-1),and the capacity retention rate is 83%after 500 cycles.

CdS/polymer S‐scheme H_(2)‐production photocatalyst and its in‐situ irradiated electron transfer mechanism

Hydrogen(H_(2))is a clean,efficient,and renewable energy with zero carbon emission,which is expected to replace the extensively used fossil fuels.Photocatalytic water splitting is a promising strategy for sustainable H2 production.Nevertheless,the performance of single‐component photocatalysts is often confined by fast electron‐hole recombination due to strong Coulombic force,and their inability to simultaneously attain a wide absorption range and enough redox capabilities.These problems can be addressed by constructing a heterojunction between two semiconductors with different Fermi levels(EF),conduction band(CB)and valence band(VB)positions.Heterojunction promotes light harvesting through light absorption on both semiconductors and facilitates charge separation by decoupling them on different bands.There are mainly three types of heterojunctions,namely the type‐II heterojunction,the Z‐scheme heterojunction,and the step‐scheme(S‐scheme)heterojunction[1–3].In a type‐II heterojunction,photogenerated electrons migrate from the higher CB to the lower one,while photogenerated holes transfer from the lower to the higher VB.However,this schematic is thermodynamically flawed since the charge transfer discounts the redox powers of the electrons and holes.This transfer is also dynamically unfavorable due to strong repulsion between the photogenerated electrons(or holes)in different semiconductors.The Z‐scheme heterojunction utilizes dissolved redox ion pairs(traditional Z‐scheme)or conductive materials(all‐solid‐state Z‐scheme)as the shuttle for charge transfer and separation.However,the photogenerated carriers with stronger redox powers would preferentially react with the ion pairs or combine at the conductor because of stronger driving forces,leading to deducted redox powers and reduced photocatalytic activity.S‐scheme heterojunction could avoid these drawbacks and has exhibited excellent performance in organics degradation[4,5],CO_(2) reduction[6,7],hydrogen evolution[8],etc.

Layered double hydroxide photocatalysts for solar fuel production

Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.

Photocatalytic degradation of Brilliant Green dye using CdSe quantum dots hybridized with graphene oxide under sunlight irradiation

CdSe quantum dots(QDs)hybridized with graphene oxide(GO)are synthesized by a facile chemical precipitation method.The absorption of the CdSe/GO nanocomposite is increased with a significantblue shift with respect to CdSe QDs.The specific surface area of the CdSe/GO nanocomposite is10.4m2/g,which is higher than that of CdSe QDs(5m2/g).The PL intensity of the CdSe/GO nanocomposite is lower than that of the CdSe QDs owing to the inhibition of the recombination of electron‐hole pairs in the composite.In Raman analysis,the two bands of the CdSe/GO nanocomposite are shifted to higher wavenumbers with respect to graphene oxide,which is attributed to electron injection that is induced by CdSe QDs into graphene oxide.Using the Brilliant Green dye,the photocatalytic reduction efficiency of CdSe QDs and the CdSe/GO nanocomposite under sunlight irradiation for90min are approximately81.9%and95.5%,respectively.The calculated photodegradation rate constants for CdSe QDs and the CdSe/GO nanocomposite are0.0190min–1and0.0345min–1,respectively.The enhanced photocatalytic activity of the CdSe/GO nanocomposite can be attributed to the high specific surface area and the reduction of electron‐hole pair recombination because of the introduction of graphene oxide.

Electron transfer kinetics in CdS/Pt heterojunction photocatalyst during water splitting

Noble metal cocatalysts have shown great potential in boosting the performance of CdS in photocatalytic water splitting.However,the mechanism and kinetics of electron transfer in noble-metal-decorated CdS during practical hydrogen evolution is not clearly elucidated.Herein,Pt-nanoparticle-decorated CdS nanorods(CdS/Pt)are utilized as the model system to analyze the electron transfer kinetics in CdS/Pt heterojunction.Through femtosecond transient absorption spectroscopy,three dominating exciton quenching pathways are observed and assigned to the trapping of photogenerated electrons at shallow states,recombination of free electrons and trapped holes,and radiative recombination of locally photogenerated electron-hole pairs.The introduction of Pt cocatalyst can release the electrons trapped at the shallow states and construct an ultrafast electron transfer tunnel at the CdS/Pt interface.When CdS/Pt is dispersed in acetonitrile,the lifetime and rate for interfacial electron transfer are respectively calculated to be~5.5 ps and~3.5×10^(10) s^(−1).The CdS/Pt is again dispersed in water to simulate photocatalytic water splitting.The lifetime of the interfacial electron transfer decreases to~5.1 ps and the electron transfer rate increases to~4.9×10^(10) s^(−1),confirming that Pt nanoparticles serve as the main active sites of hydrogen evolution.This work reveals the role of Pt cocatalysts in enhancing the photocatalytic performance of CdS from the perspective of electron transfer kinetics.

Palladium-copper nanodot as novel H_(2)-evolution cocatalyst:Optimizing interfacial hydrogen desorption for highly efficient photocatalytic activity

Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen‐adsorption strength to improve its interfacial H_(2)‐evolution rate via the Pd‐Cu alloying effect.Herein,the ultrasmall Pd_(100−x)Cu_(x) alloy nanodots(2−5 nm)as a novel H_(2)‐evolution cocatalyst were integrated with the TiO_(2) through a simple NaH_(2)PO_(2)‐mediated co‐deposition route.The resulting Pd_(100−x)Cu_(x)/TiO_(2) sample shows the significantly enhanced photocatalytic H_(2)‐generation performance(269.2μmol h^(−1)),which is much higher than the bare TiO2.Based on in situ irradiated X‐ray photoelectron spectroscopy(ISI‐XPS)and density functional theory(DFT)results,the as‐formed Pd_(100−x)Cu_(x) alloy nanodots can effectively promote the separation of photo‐generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen‐desorption process on Pd_(75)Cu_(25) alloy,thus leading to high photocatalytic H_(2)‐evolution activity.Herein,the weakened H adsorption of Pd_(75)Cu_(25) cocatalyst can be ascribed to the formation of electron‐rich Pd after the introduction of weak electronegativity Cu.The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.

Revealing Photoinduced Charge Transfer Mechanism of SnO2/BiOBr SScheme Heterostructure for CO_(2)Photoreduction

S-scheme heterojunctions can preserve strong redox capacity on the basis of achieving spatial separation of photogenerated carriers.Therefore,a deep comprehension of the photoinduced charge transfer dynamics in S-scheme heterostructures is vital to enhancing photocatalytic properties.Herein,SnO_(2)/BiOBr S-scheme heterojunctions with tight contact are fabricated with in situ hydrothermal method.The optimal SnO_(2)/BiOBr exhibits excellent photocatalytic performance for CO_(2)reduction,with yields of CO and CH4 of 345.7 and 6.7μmol∙g^(–1)∙h^(–1),which are 5.6 and 3.7 times higher than those of the original BiOBr.The photoinduced charge transfer mechanism and dynamics of SnO_(2)/BiOBr S-scheme heterostructure are characterized by in situ X-ray photoelectron spectrum(XPS)and femtosecond transient absorption spectroscopy(fs-TA).A new fitted lifetime of photogenerated carriers are observed,which could be attributed to interfacial electron transfer of S-scheme heterojunction,further illustrating an ultrafast transfer channel for photoelectrons from SnO_(2)conduction band to BiOBr valence band.As a result,the powerful reduced electrons in BiOBr conduction band and the powerful oxidation holes in SnO_(2)valence band are retained.This work provides profound comprehension of photoinduced charge transfer mechanism of S-scheme heterojunction.