A model for describing solute segregation at grain boundaries has been developed for substitutional solid solution alloys,which integrates multiple factors from atomic to microstructural scales.A concept of mo-lar Gib...A model for describing solute segregation at grain boundaries has been developed for substitutional solid solution alloys,which integrates multiple factors from atomic to microstructural scales.A concept of mo-lar Gibbs free energy of segregation was introduced to evaluate the segregating capability of the solute elements in a closed system,through which the influences of grain boundary structure,grain size,ma-terial composition,and external conditions were described.Based on the evaluation of various energy forms related to solute segregation and grain growth processes,the nature of the thermal stabilization of nanograin structures by solute segregation was disclosed.A criterion for the destabilization of nanostruc-tures,which is determined by the competition of the change rates between the molar Gibbs free energy of segregation and the total energy of grain boundaries with grain size,has been proposed.This study provided guideline to achieve high-temperature stability of nanograin structures of solid solution alloys even for the weakly segregating nanocrystalline systems.展开更多
Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behav...Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.展开更多
Rare-earth hexaborides(REB_(6))are vital raw materials for cathode materials and high temperature structural ceramics that are widely applied as high-frequency electron tubes and ceramics adaptive for extreme environm...Rare-earth hexaborides(REB_(6))are vital raw materials for cathode materials and high temperature structural ceramics that are widely applied as high-frequency electron tubes and ceramics adaptive for extreme environment,respectively.In this work,single phase substitutional solid solution REB_(6)(LaB_(6),La_(0.75)Ce_(0.25)B_(6).La_(0.5)Ce_(0.5)B_(6),La_(0.25)Ce_(0.75)B_(6) and CeB_(6))powders were prepared with the raw materials of La_(2)O_(3),CeO_(2),B_(4)C and Al powders,after calcining at 1773 K for 4 h and the following alkaline leaching.All substitutional solid solution products have homogeneous distributions of La and Ce in particles.Through microscopic morphology analysis,it is discovered that the formation of solid solution is beneficial for reducing the particle size of product,relative to LaB_(6) and CeB_(6).Moreover,Al flux plays an important role in decarbonizing reaction,and C contents of all products are below 0.4 wt%.展开更多
This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prep...This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prepared by recrystallization annealing after cold pressing,although the alloys with stoichiometric and hyperstoichiometric compositions remain brittle.Melt-spun ribbons with hypostoichiometric compositions contain fine anti-phase domains (APDs),while no APD can be seen in melt-spun ribbons with a hyperstoichiometric composition.The ductility in hypostoichiometric Ni_3Al alloys is associated with low ordering energy of the alloys.The addition of ternary elements,which have been classified as γ formers such as Pd,Pt,Cu,Co and Ag.improves ductility of Ni_3Al alloys.Correspondingly,the microstructure of the melt-spun ribbons consists of fine APDs.The addition of γ' formers such as Si,Ti,Zr,V,Nb and Ta leads to brittle intergranular frac- ture.No APD was observed in the melt-spun ribbons of these ternary alloys.展开更多
Based on ab initio calculations,it is found that the donor center of substitutional sulfur(S)in diamond with C2v symmetry is more stable than that with C3vsymmetry,which is different from previous reports in literatur...Based on ab initio calculations,it is found that the donor center of substitutional sulfur(S)in diamond with C2v symmetry is more stable than that with C3vsymmetry,which is different from previous reports in literature.The energy difference of C2vand C3vstructures is qualitatively affected by the supercell size,and the 216-atom supercell could be proposed as the minimum to obtain stable configuration of substitutional S in diamond.Using supercells of up to 512 atoms,the donor level of substitutional S with C2vsymmetry is deep.展开更多
Using first-principles calculations based on density functional theory,we show that the ground state of zigzag-edged graphene nanoribbons(ZGNRs)can be transformed from antiferromagnetic(AFM)order to ferromagnetic(FM)o...Using first-principles calculations based on density functional theory,we show that the ground state of zigzag-edged graphene nanoribbons(ZGNRs)can be transformed from antiferromagnetic(AFM)order to ferromagnetic(FM)order by changing the substitutional sites of N or B dopants.This AFM–FM transition induced by substitutional sites is found to be a consequence of the competition between the edge and bulk states.The energy sequence of the edge and bulk states near the Fermi level is reversed in the AFM and FM configurations.When the dopant is substituted near the edge of the ribbon,the extra charge from the dopant is energetically favorable to occupy the edge states in AFM configuration.When the dopant is substituted near the center,the extra charge is energetically favorable to occupy the bulk states in FM configuration.Proper substrate with weak interaction is necessary to maintain the magnetic properties of the doped ZGNRs.Our study can serve as a guide to synthesize graphene nanostructures with stable FM order for future applications to spintronic devices.展开更多
Two-dimensional(2D)van der Waals transition metal dichalcogenides(TMDs)are a new class of electronic materials offering tremendous opportunities for advanced technologies and fundamental studies.Similar to conventiona...Two-dimensional(2D)van der Waals transition metal dichalcogenides(TMDs)are a new class of electronic materials offering tremendous opportunities for advanced technologies and fundamental studies.Similar to conventional semiconductors,substitutional doping is key to tailoring their electronic properties and enabling their device applications.Here,we review recent progress in doping methods and understanding of doping effects in group 6 TMDs(MX2,M=Mo,W;X=S,Se,Te),which are the most widely studied model 2D semiconductor system.Experimental and theoretical studies have shown that a number of different elements can substitute either M or X atoms in these materials and act as n-or p-type dopants.This review will survey the impact of substitutional doping on the electrical and optical properties of these materials,discuss open questions,and provide an outlook for further studies.展开更多
Substitutional atomic doping of transition metal dichalcogenides(TMDs)in the chemical vapor deposition(CVD)process is a promising and effective strategy for modifying their physicochemical properties.However,the conve...Substitutional atomic doping of transition metal dichalcogenides(TMDs)in the chemical vapor deposition(CVD)process is a promising and effective strategy for modifying their physicochemical properties.However,the conventional CVD method only allows narrow-range modulation of the dopant concentration owing to the low reactivity of the precursors.Moreover,the growth of wafer-scale monolayer TMD films with high dopant concentrations is much more challenging.Herein,we report a facile doping approach based on liquid precursor-mediated CVD process for achieving high vanadium(V)doping in the MoS_(2)lattice with excellent doping uniformity and stability.The lateral growth of the host MoS_(2)lattice and the reactivity of the V precursor were simultaneously improved by introducing an alkali metal halide as a reaction promoter.The metal halide promoter enabled the wafer-scale synthesis of V-incorporated MoS_(2)monolayer film with excessively high doping concentrations.The excellent wafer-scale uniformity of the highly V-doped MoS_(2)film was confirmed through a series of microscopic,spectroscopic,and electrical analyses.展开更多
Neutron-transmutation doping(NTD)has been demonstrated for the first time in this work for substitutional introduction of tin(Sn)shallow donors into two-dimensional(2D)layered indium selenide(InSe)to manipulate electr...Neutron-transmutation doping(NTD)has been demonstrated for the first time in this work for substitutional introduction of tin(Sn)shallow donors into two-dimensional(2D)layered indium selenide(InSe)to manipulate electron transfer and charge carrier dynamics.Multidisciplinary study including density functional theory,transient optical absorption,and FET devices have been carried out to reveal that the field effect electron mobility of the fabricated phototransistor is increased 100-fold due to the smaller electron effective mass and longer electron life time in the Sn-doped InSe.The responsivity of the Sn-doped InSe based phototransistor is accordingly enhanced by about 50 times,being as high as 397 A/W.The results show that NTD is a highly effective and controllable doping method,possessing good compatibility with the semiconductor manufacturing process,even after device fabrication,and can be carried out without introducing any contamination,which is radically different from traditional doping methods.展开更多
A medical image encryption is proposed based on the Fisher-Yates scrambling,filter diffusion and S-box substitution.First,chaotic sequence associated with the plaintext is generated by logistic-sine-cosine system,whic...A medical image encryption is proposed based on the Fisher-Yates scrambling,filter diffusion and S-box substitution.First,chaotic sequence associated with the plaintext is generated by logistic-sine-cosine system,which is used for the scrambling,substitution and diffusion processes.The three-dimensional Fisher-Yates scrambling,S-box substitution and diffusion are employed for the first round of encryption.The chaotic sequence is adopted for secondary encryption to scramble the ciphertext obtained in the first round.Then,three-dimensional filter is applied to diffusion for further useful information hiding.The key to the algorithm is generated by the combination of hash value of plaintext image and the input parameters.It improves resisting ability of plaintext attacks.The security analysis shows that the algorithm is effective and efficient.It can resist common attacks.In addition,the good diffusion effect shows that the scheme can solve the differential attacks encountered in the transmission of medical images and has positive implications for future research.展开更多
Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N c...Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N catalysis.Monosubstitu-tion C—N bond formation reaction catalyzed by K_(2)CO_(3) also gave novel enol-based target products.This method is simple and mild,with good chemoselectivity,excellent substrate compatibility and tolerance for various functional groups,and achieves gram-scale synthesis.The reaction is a nucleophilic substitution process without the involvement of free radicals.展开更多
Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution o...Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.展开更多
A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported,enabling highly diastereoselective access to cyclic etherified cyclopentenones w...A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported,enabling highly diastereoselective access to cyclic etherified cyclopentenones with cyclic quaternary centers in moderate to good yields and>19∶1 dr.This catalysis enables the direct construction of two types of carboncyclic skeletons by adjusting the olefin types of 1,3-enyne acetates.When 1,3-enyne acetates bearing a cyclic alkene unit were used,5~6 fused bicarbocyclic products were diastereoselectively synthesized,whereas the reaction of acyclic 1,3-enyne acetates resulted in five-memebered carbocyclic framework.Notably,cyclic ether acetals are commonly used as protecting groups in traditional multistep organic syntheses,and in this reaction,such reagents serve as electrophilic cyclic ether precursors,achieving new uses for old reagents.The current method demonstrates good functional group compatibility,a broad substrate scope and high diastereoselectivity,providing a new synthetic strategy toward functionalized cyclopentenones.展开更多
The feldspar-based microwave dielectric ceramic with low relative permittivity(εr)and excellent mechanical properties has attracted much attention in the fifth-generation wireless communication technology.In this wor...The feldspar-based microwave dielectric ceramic with low relative permittivity(εr)and excellent mechanical properties has attracted much attention in the fifth-generation wireless communication technology.In this work,a series of microwave dielectric ceramic SrAl_(2-x)Ga_(x)Si_(2)O_(8)(0.1≤x≤2.0)was synthesized using the traditional solid-state method.X-ray diffraction pattern indicates that Ga^(3+)can be dissolved into Al^(3+),forming a solid solution.Meanwhile,substitution of Ga^(3+)for Al^(3+)can promote the space group transition from I2/c(0.1≤x≤1.4)to P21/a(1.6≤x≤2.0)with coefficient of thermal expansion(CTE)increasing from 2.9×10^(-6)℃^(-1) to 5.2×10^(-6)℃^(-1).During this substitution,the phase transition can significantly improve the structural symmetry to enhance the dielectric properties and mechanical properties.Rietveld refinement results indicate that Ga^(3+)averagely occupied four Al^(3+)compositions to form solid solution.All ceramics have a dense microstructure and high relative density above 95%.An ultralower of 5.8 was obtained at x=1.6 composition with high quality factor(Q´f)of 50700 GHz and negative temperature coefficients of resonant frequency(tf)of approximately−35×10^(-6)℃^(-1).The densification temperature can be reduced to 940℃by adding 4%(in mass)LiF,resulting in good chemical compatibility with Ag electrode.Meanwhile,negativetf can be tuned to near-zero(+3.7×10^(-6)℃^(-1))by adding CaTiO_(3) ceramic.展开更多
Photofragmentation study of metal fullerides C60Mx (M=Sm, Pt, Ni and Rh) by excimer laser ablation-TOF mass spectrometry shows that metallofullerenes C2nM and C2n+1M formed in both the positive and negative ionic mode...Photofragmentation study of metal fullerides C60Mx (M=Sm, Pt, Ni and Rh) by excimer laser ablation-TOF mass spectrometry shows that metallofullerenes C2nM and C2n+1M formed in both the positive and negative ionic modes. The isotopic distributions of the metallofullerenes C2nM and C2n+1M are consistent with the calculated spectra based on the natural abundance of isotopes of C and M, confirming the formation of metallofullerenes. The metal atom is sup-posed to be incorporated into the network of the fullerene cage to replace one carbon atom of the cage forming substi-tutional metallofullerene. Odd-numbered high carbon clusters are observed in our laser ablation study of all the metal fullerides in the negative ion channel. Evolution of mass spectrum with irradiation laser shots shows that the formation of the substitutionally doped fullerenes is closely related to the production of metal carbide (MC). The structures, as well as formation mechanism, of metallofullerenes C2n+1M and C2nM with even and odd展开更多
On account of the integral behavior of dislocations and the interaction between solute atoms and dislocations, a model describing the serrated yielding (i.e. the PL effect) in substitutional alloys is proposed. Accord...On account of the integral behavior of dislocations and the interaction between solute atoms and dislocations, a model describing the serrated yielding (i.e. the PL effect) in substitutional alloys is proposed. According to this model, the serrated yielding occurring in a certain strain rate-temperature range will disappear when the strain exceeds a proper value under certain conditions. The model has been confirmed by tensile tests and rapid changing strain rate tests on a commercial Cu-32wt.％ Zn alloy. Experimental results agree well with the predicted effects of temperature and strain rate on the critical strain for the appearance and disappearance of serrations.展开更多
Industrial waste management constitutes a major challenge for sustainable development. This study aims to transform hardened cement waste stored in cement warehouses and in real estate construction sites into paving s...Industrial waste management constitutes a major challenge for sustainable development. This study aims to transform hardened cement waste stored in cement warehouses and in real estate construction sites into paving stones. This innovative solution will contribute to the protection of the environment and the reduction of inert industrial waste. To do this, paving stones based on hardened cement have been developed and characterized. The raw materials were subjected to physical and mechanical characterization tests. The hardened cement aggregates previously crushed with the 5/15 granular class were used as substitutes to replace the natural 5/15 aggregates in the hardened paving stones at contents ranging from 0 to 100%. The mechanical characterization results on the raw material showed that the hardened cement aggregate is made from lightweight aggregates. On the prepared mortar, in the fresh state, the Abrams cone slump test showed an increase in the quantity of waste water with the increase in the content of hardened cement aggregate. In the hardened state, physical (porosity, absorption and dry density) and mechanical (compression, splitting traction, 3-point bending traction and wear) characterization tests were carried out at periods of 7, 14 and 28 days of maturation in water on the cobblestones. These results show that the substitution of natural aggregates by hardened cement aggregates in increasingly large proportions leads to an improvement in compressive, flexural, splitting and wear resistance. In addition, the incorporation of hardened cement aggregate considerably slows down the mechanical degradation of the paving stones. They can, therefore, be used in road and interior or exterior floor coverings.展开更多
Bioprinting is a widely used technique for creating three-dimensional,complex,and heterogeneous artificial tissue constructs that are biologically and biophysically similar to natural tissues.The skin is composed of s...Bioprinting is a widely used technique for creating three-dimensional,complex,and heterogeneous artificial tissue constructs that are biologically and biophysically similar to natural tissues.The skin is composed of several layers including the epidermis,basement membrane(BM),and dermis.However,the unique undulating structure of basement membranes(i.e.rete ridges)and the function of BM have not been extensively studied in the fabrication of engineered skin substitutes.In this study,a novel engineered skin substitute incorporating an artificially designed rete ridge(i.e.mogul-shape)was developed using bioprinting and bioinks prepared using collagen and fibrinogen.To mimic the structure of the rete ridges of skin tissue,we developed a modified bioprinting technique,controlling rheological property of bioink to create a mogul-shaped layer.In vitro cellular activities,including the expression of specific genes(those encoding vimentin,laminin-5,collagen IV,and cytokeratins),demonstrated that the engineered skin substitute exhibited more potent cellular responses than the normally bioprinted control owing to the favorable biophysical BM structure and the bioink microenvironment.Additionally,the feasibility of utilizing the bioprinted skin-structure was evaluated in a mouse model,and in vivo results demonstrated that the bioprinted skin substitutes effectively promoted wound healing capabilities.Based on these results,we suggest that bioprinted skin tissues and the bioprinting technique for mimicking rete ridges can be used not only as potential lab-chip models for testing cosmetic materials and drugs,but also as complex physiological models for understanding human skin.展开更多
Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such ...Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.展开更多
Alloy engineering,with its ability to tune the electronic band structure,is regarded as an effective method for adjusting the electronic and optoelectronic properties of two-dimensional(2D)semiconductors.However,synth...Alloy engineering,with its ability to tune the electronic band structure,is regarded as an effective method for adjusting the electronic and optoelectronic properties of two-dimensional(2D)semiconductors.However,synthesizing metal-site substitution alloys remains challenging due to the low reactivity of metal precursors and the tendency for spatial phase separation during high-temperature growth.Here,we report the preparation of a high-quality metal-site substitution alloy,Zn_(0.167)Sn_(0.833)S_(2),via the chemical vapor transport method,which exhibits excellent photoresponsivity and enhanced electrical transport properties.Comprehensive characterization techniques,including Raman spectroscopy,x-ray photoelectron spectroscopy(XPS),and electron microscopy,unambiguously confirm the uniform Zn substitution in the as-prepared Zn_(0.167)Sn_(0.833)S_(2) alloy.Furthermore,the photodetector based on the Zn_(0.167)Sn_(0.833)S_(2) alloy demonstrated a high on/off ratio of 51 under white light,a wide spectral response range from 350 nm to 900 nm,and a broad dynamic power range of 80 dB under 638-nm illumination.In terms of transport properties,field-effect transistors(FETs)based on Zn_(0.167)Sn_(0.833)S_(2) achieved a carrier mobility of 6.5 cm^(2)·V^(-1)·s^(-1),which is six times higher than that of SnS_(2).This alloy semiconductor showcases significantly enhanced electronic and optoelectronic properties,offering great potential for the development of high-resolution photodetection technologies.展开更多
基金supported by the Beijing Natural Science Foun-dation(No.2214067)the National Key R&D Program of China(Nos.2021YFB3501502 and 2021YFB3501504)the National Natural Science Foundation of China(No.92163107).
文摘A model for describing solute segregation at grain boundaries has been developed for substitutional solid solution alloys,which integrates multiple factors from atomic to microstructural scales.A concept of mo-lar Gibbs free energy of segregation was introduced to evaluate the segregating capability of the solute elements in a closed system,through which the influences of grain boundary structure,grain size,ma-terial composition,and external conditions were described.Based on the evaluation of various energy forms related to solute segregation and grain growth processes,the nature of the thermal stabilization of nanograin structures by solute segregation was disclosed.A criterion for the destabilization of nanostruc-tures,which is determined by the competition of the change rates between the molar Gibbs free energy of segregation and the total energy of grain boundaries with grain size,has been proposed.This study provided guideline to achieve high-temperature stability of nanograin structures of solid solution alloys even for the weakly segregating nanocrystalline systems.
基金This work was supported by National Key R&D Program of China(2021YFF1200200)Peiyang Talents Project of Tianjin University.
文摘Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.
基金financially supported by State Key Laboratory of Advanced Metallurgy,University of Science and Technology Beijing,China。
文摘Rare-earth hexaborides(REB_(6))are vital raw materials for cathode materials and high temperature structural ceramics that are widely applied as high-frequency electron tubes and ceramics adaptive for extreme environment,respectively.In this work,single phase substitutional solid solution REB_(6)(LaB_(6),La_(0.75)Ce_(0.25)B_(6).La_(0.5)Ce_(0.5)B_(6),La_(0.25)Ce_(0.75)B_(6) and CeB_(6))powders were prepared with the raw materials of La_(2)O_(3),CeO_(2),B_(4)C and Al powders,after calcining at 1773 K for 4 h and the following alkaline leaching.All substitutional solid solution products have homogeneous distributions of La and Ce in particles.Through microscopic morphology analysis,it is discovered that the formation of solid solution is beneficial for reducing the particle size of product,relative to LaB_(6) and CeB_(6).Moreover,Al flux plays an important role in decarbonizing reaction,and C contents of all products are below 0.4 wt%.
文摘This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prepared by recrystallization annealing after cold pressing,although the alloys with stoichiometric and hyperstoichiometric compositions remain brittle.Melt-spun ribbons with hypostoichiometric compositions contain fine anti-phase domains (APDs),while no APD can be seen in melt-spun ribbons with a hyperstoichiometric composition.The ductility in hypostoichiometric Ni_3Al alloys is associated with low ordering energy of the alloys.The addition of ternary elements,which have been classified as γ formers such as Pd,Pt,Cu,Co and Ag.improves ductility of Ni_3Al alloys.Correspondingly,the microstructure of the melt-spun ribbons consists of fine APDs.The addition of γ' formers such as Si,Ti,Zr,V,Nb and Ta leads to brittle intergranular frac- ture.No APD was observed in the melt-spun ribbons of these ternary alloys.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11704143,51672102,51632002,and 11604023)the National Key Research and Development Program of China(Grant Nos.2018YFA0305900 and 2016YFB0201204)the Program for Changjiang Scholars and Innovative Research Team in University(Grant No.IRT-15R23)
文摘Based on ab initio calculations,it is found that the donor center of substitutional sulfur(S)in diamond with C2v symmetry is more stable than that with C3vsymmetry,which is different from previous reports in literature.The energy difference of C2vand C3vstructures is qualitatively affected by the supercell size,and the 216-atom supercell could be proposed as the minimum to obtain stable configuration of substitutional S in diamond.Using supercells of up to 512 atoms,the donor level of substitutional S with C2vsymmetry is deep.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11474274 and 61427901)the National Basic Research Program of China(Grant No.2014CB643902)
文摘Using first-principles calculations based on density functional theory,we show that the ground state of zigzag-edged graphene nanoribbons(ZGNRs)can be transformed from antiferromagnetic(AFM)order to ferromagnetic(FM)order by changing the substitutional sites of N or B dopants.This AFM–FM transition induced by substitutional sites is found to be a consequence of the competition between the edge and bulk states.The energy sequence of the edge and bulk states near the Fermi level is reversed in the AFM and FM configurations.When the dopant is substituted near the edge of the ribbon,the extra charge from the dopant is energetically favorable to occupy the edge states in AFM configuration.When the dopant is substituted near the center,the extra charge is energetically favorable to occupy the bulk states in FM configuration.Proper substrate with weak interaction is necessary to maintain the magnetic properties of the doped ZGNRs.Our study can serve as a guide to synthesize graphene nanostructures with stable FM order for future applications to spintronic devices.
基金the Ministry of Education(MOE),Singapore,under AcRF Tier 3(MOE2018-T3-1-005)the Singapore National Research Foundation for funding the research under medium-sized centre programme.M.B.acknowledges support from MOE’s AcRF Tier 1(R-284-000-179-133).
文摘Two-dimensional(2D)van der Waals transition metal dichalcogenides(TMDs)are a new class of electronic materials offering tremendous opportunities for advanced technologies and fundamental studies.Similar to conventional semiconductors,substitutional doping is key to tailoring their electronic properties and enabling their device applications.Here,we review recent progress in doping methods and understanding of doping effects in group 6 TMDs(MX2,M=Mo,W;X=S,Se,Te),which are the most widely studied model 2D semiconductor system.Experimental and theoretical studies have shown that a number of different elements can substitute either M or X atoms in these materials and act as n-or p-type dopants.This review will survey the impact of substitutional doping on the electrical and optical properties of these materials,discuss open questions,and provide an outlook for further studies.
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Korea government(MSIT)(Nos.2019R1A2C1009025 and 2022R1A4A2000823)2022 research Fund(No.1.220024.01)of Ulsan National Institute of Science&Technology(UNIST).
文摘Substitutional atomic doping of transition metal dichalcogenides(TMDs)in the chemical vapor deposition(CVD)process is a promising and effective strategy for modifying their physicochemical properties.However,the conventional CVD method only allows narrow-range modulation of the dopant concentration owing to the low reactivity of the precursors.Moreover,the growth of wafer-scale monolayer TMD films with high dopant concentrations is much more challenging.Herein,we report a facile doping approach based on liquid precursor-mediated CVD process for achieving high vanadium(V)doping in the MoS_(2)lattice with excellent doping uniformity and stability.The lateral growth of the host MoS_(2)lattice and the reactivity of the V precursor were simultaneously improved by introducing an alkali metal halide as a reaction promoter.The metal halide promoter enabled the wafer-scale synthesis of V-incorporated MoS_(2)monolayer film with excessively high doping concentrations.The excellent wafer-scale uniformity of the highly V-doped MoS_(2)film was confirmed through a series of microscopic,spectroscopic,and electrical analyses.
基金State Key Research Development Program of China(Grant No.2019YFB2203503)National Natural Science Fund(Grant Nos.61875138,61961136001,62104153,62105211 and U1801254)+2 种基金Natural Science Foundation of Guangdong Province(2018B030306038 and 2020A1515110373)Science and Technology Innovation Commission of Shenzhen(JCYJ20180507182047316 and 20200805132016001)Postdoctoral Science Foundation of China(No.2021M702237)。
文摘Neutron-transmutation doping(NTD)has been demonstrated for the first time in this work for substitutional introduction of tin(Sn)shallow donors into two-dimensional(2D)layered indium selenide(InSe)to manipulate electron transfer and charge carrier dynamics.Multidisciplinary study including density functional theory,transient optical absorption,and FET devices have been carried out to reveal that the field effect electron mobility of the fabricated phototransistor is increased 100-fold due to the smaller electron effective mass and longer electron life time in the Sn-doped InSe.The responsivity of the Sn-doped InSe based phototransistor is accordingly enhanced by about 50 times,being as high as 397 A/W.The results show that NTD is a highly effective and controllable doping method,possessing good compatibility with the semiconductor manufacturing process,even after device fabrication,and can be carried out without introducing any contamination,which is radically different from traditional doping methods.
文摘A medical image encryption is proposed based on the Fisher-Yates scrambling,filter diffusion and S-box substitution.First,chaotic sequence associated with the plaintext is generated by logistic-sine-cosine system,which is used for the scrambling,substitution and diffusion processes.The three-dimensional Fisher-Yates scrambling,S-box substitution and diffusion are employed for the first round of encryption.The chaotic sequence is adopted for secondary encryption to scramble the ciphertext obtained in the first round.Then,three-dimensional filter is applied to diffusion for further useful information hiding.The key to the algorithm is generated by the combination of hash value of plaintext image and the input parameters.It improves resisting ability of plaintext attacks.The security analysis shows that the algorithm is effective and efficient.It can resist common attacks.In addition,the good diffusion effect shows that the scheme can solve the differential attacks encountered in the transmission of medical images and has positive implications for future research.
文摘Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N catalysis.Monosubstitu-tion C—N bond formation reaction catalyzed by K_(2)CO_(3) also gave novel enol-based target products.This method is simple and mild,with good chemoselectivity,excellent substrate compatibility and tolerance for various functional groups,and achieves gram-scale synthesis.The reaction is a nucleophilic substitution process without the involvement of free radicals.
文摘Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.
文摘A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported,enabling highly diastereoselective access to cyclic etherified cyclopentenones with cyclic quaternary centers in moderate to good yields and>19∶1 dr.This catalysis enables the direct construction of two types of carboncyclic skeletons by adjusting the olefin types of 1,3-enyne acetates.When 1,3-enyne acetates bearing a cyclic alkene unit were used,5~6 fused bicarbocyclic products were diastereoselectively synthesized,whereas the reaction of acyclic 1,3-enyne acetates resulted in five-memebered carbocyclic framework.Notably,cyclic ether acetals are commonly used as protecting groups in traditional multistep organic syntheses,and in this reaction,such reagents serve as electrophilic cyclic ether precursors,achieving new uses for old reagents.The current method demonstrates good functional group compatibility,a broad substrate scope and high diastereoselectivity,providing a new synthetic strategy toward functionalized cyclopentenones.
基金National Natural Science Foundation of China (52302140)Major Scientific and Technological Innovation Project of Wenzhou (ZG2023040, ZG2023042)Joint Funds of the National Natural Science Foundation of China Key Program (U21B2068)。
文摘The feldspar-based microwave dielectric ceramic with low relative permittivity(εr)and excellent mechanical properties has attracted much attention in the fifth-generation wireless communication technology.In this work,a series of microwave dielectric ceramic SrAl_(2-x)Ga_(x)Si_(2)O_(8)(0.1≤x≤2.0)was synthesized using the traditional solid-state method.X-ray diffraction pattern indicates that Ga^(3+)can be dissolved into Al^(3+),forming a solid solution.Meanwhile,substitution of Ga^(3+)for Al^(3+)can promote the space group transition from I2/c(0.1≤x≤1.4)to P21/a(1.6≤x≤2.0)with coefficient of thermal expansion(CTE)increasing from 2.9×10^(-6)℃^(-1) to 5.2×10^(-6)℃^(-1).During this substitution,the phase transition can significantly improve the structural symmetry to enhance the dielectric properties and mechanical properties.Rietveld refinement results indicate that Ga^(3+)averagely occupied four Al^(3+)compositions to form solid solution.All ceramics have a dense microstructure and high relative density above 95%.An ultralower of 5.8 was obtained at x=1.6 composition with high quality factor(Q´f)of 50700 GHz and negative temperature coefficients of resonant frequency(tf)of approximately−35×10^(-6)℃^(-1).The densification temperature can be reduced to 940℃by adding 4%(in mass)LiF,resulting in good chemical compatibility with Ag electrode.Meanwhile,negativetf can be tuned to near-zero(+3.7×10^(-6)℃^(-1))by adding CaTiO_(3) ceramic.
基金This work was supported by the National Natural Science Foundation of China (Grant No. Project 29890216).
文摘Photofragmentation study of metal fullerides C60Mx (M=Sm, Pt, Ni and Rh) by excimer laser ablation-TOF mass spectrometry shows that metallofullerenes C2nM and C2n+1M formed in both the positive and negative ionic modes. The isotopic distributions of the metallofullerenes C2nM and C2n+1M are consistent with the calculated spectra based on the natural abundance of isotopes of C and M, confirming the formation of metallofullerenes. The metal atom is sup-posed to be incorporated into the network of the fullerene cage to replace one carbon atom of the cage forming substi-tutional metallofullerene. Odd-numbered high carbon clusters are observed in our laser ablation study of all the metal fullerides in the negative ion channel. Evolution of mass spectrum with irradiation laser shots shows that the formation of the substitutionally doped fullerenes is closely related to the production of metal carbide (MC). The structures, as well as formation mechanism, of metallofullerenes C2n+1M and C2nM with even and odd
基金Project supported by the National Natural Science Foundation of China and the Natural Science Fund of Fujian, China.
文摘On account of the integral behavior of dislocations and the interaction between solute atoms and dislocations, a model describing the serrated yielding (i.e. the PL effect) in substitutional alloys is proposed. According to this model, the serrated yielding occurring in a certain strain rate-temperature range will disappear when the strain exceeds a proper value under certain conditions. The model has been confirmed by tensile tests and rapid changing strain rate tests on a commercial Cu-32wt.％ Zn alloy. Experimental results agree well with the predicted effects of temperature and strain rate on the critical strain for the appearance and disappearance of serrations.
文摘Industrial waste management constitutes a major challenge for sustainable development. This study aims to transform hardened cement waste stored in cement warehouses and in real estate construction sites into paving stones. This innovative solution will contribute to the protection of the environment and the reduction of inert industrial waste. To do this, paving stones based on hardened cement have been developed and characterized. The raw materials were subjected to physical and mechanical characterization tests. The hardened cement aggregates previously crushed with the 5/15 granular class were used as substitutes to replace the natural 5/15 aggregates in the hardened paving stones at contents ranging from 0 to 100%. The mechanical characterization results on the raw material showed that the hardened cement aggregate is made from lightweight aggregates. On the prepared mortar, in the fresh state, the Abrams cone slump test showed an increase in the quantity of waste water with the increase in the content of hardened cement aggregate. In the hardened state, physical (porosity, absorption and dry density) and mechanical (compression, splitting traction, 3-point bending traction and wear) characterization tests were carried out at periods of 7, 14 and 28 days of maturation in water on the cobblestones. These results show that the substitution of natural aggregates by hardened cement aggregates in increasingly large proportions leads to an improvement in compressive, flexural, splitting and wear resistance. In addition, the incorporation of hardened cement aggregate considerably slows down the mechanical degradation of the paving stones. They can, therefore, be used in road and interior or exterior floor coverings.
基金supported by the‘Korea National Institute of Health’(KNIH)research project(Project No.2022ER130502)the National Research Foundation of Korea(NRF)Grant funded by the Korea Government(MSIT)(No.2021R1A2C20060331222182102840102)。
文摘Bioprinting is a widely used technique for creating three-dimensional,complex,and heterogeneous artificial tissue constructs that are biologically and biophysically similar to natural tissues.The skin is composed of several layers including the epidermis,basement membrane(BM),and dermis.However,the unique undulating structure of basement membranes(i.e.rete ridges)and the function of BM have not been extensively studied in the fabrication of engineered skin substitutes.In this study,a novel engineered skin substitute incorporating an artificially designed rete ridge(i.e.mogul-shape)was developed using bioprinting and bioinks prepared using collagen and fibrinogen.To mimic the structure of the rete ridges of skin tissue,we developed a modified bioprinting technique,controlling rheological property of bioink to create a mogul-shaped layer.In vitro cellular activities,including the expression of specific genes(those encoding vimentin,laminin-5,collagen IV,and cytokeratins),demonstrated that the engineered skin substitute exhibited more potent cellular responses than the normally bioprinted control owing to the favorable biophysical BM structure and the bioink microenvironment.Additionally,the feasibility of utilizing the bioprinted skin-structure was evaluated in a mouse model,and in vivo results demonstrated that the bioprinted skin substitutes effectively promoted wound healing capabilities.Based on these results,we suggest that bioprinted skin tissues and the bioprinting technique for mimicking rete ridges can be used not only as potential lab-chip models for testing cosmetic materials and drugs,but also as complex physiological models for understanding human skin.
文摘Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.
基金supported by the Beijing Natural Science Foundation(Grant No.Z220005)the National Key Research and Development Program of China(Grant Nos.2022YFB3606902 and 2022YFA1405600)+1 种基金the National Natural Science Foundation of China(Grant No.12274456)the Opening Project of the Laboratory of Microelectronic Devices&Integrated Technology,Chinese Academy of Sciences(CAS),Institute of Microelectronics,Chinese Academy of Sciences.
文摘Alloy engineering,with its ability to tune the electronic band structure,is regarded as an effective method for adjusting the electronic and optoelectronic properties of two-dimensional(2D)semiconductors.However,synthesizing metal-site substitution alloys remains challenging due to the low reactivity of metal precursors and the tendency for spatial phase separation during high-temperature growth.Here,we report the preparation of a high-quality metal-site substitution alloy,Zn_(0.167)Sn_(0.833)S_(2),via the chemical vapor transport method,which exhibits excellent photoresponsivity and enhanced electrical transport properties.Comprehensive characterization techniques,including Raman spectroscopy,x-ray photoelectron spectroscopy(XPS),and electron microscopy,unambiguously confirm the uniform Zn substitution in the as-prepared Zn_(0.167)Sn_(0.833)S_(2) alloy.Furthermore,the photodetector based on the Zn_(0.167)Sn_(0.833)S_(2) alloy demonstrated a high on/off ratio of 51 under white light,a wide spectral response range from 350 nm to 900 nm,and a broad dynamic power range of 80 dB under 638-nm illumination.In terms of transport properties,field-effect transistors(FETs)based on Zn_(0.167)Sn_(0.833)S_(2) achieved a carrier mobility of 6.5 cm^(2)·V^(-1)·s^(-1),which is six times higher than that of SnS_(2).This alloy semiconductor showcases significantly enhanced electronic and optoelectronic properties,offering great potential for the development of high-resolution photodetection technologies.
