锂钠比对碱铝硅酸盐玻璃的化学强化性能影响

采用熔融淬冷法制备了不同锂钠比的锂铝硅酸盐玻璃,用两步化学强化法对样品进行了化学强化处理,研究了Li_(2)O取代Na_(2)O对铝硅酸盐玻璃机械性能和化学强化特征参数的影响。结果表明:随着Li_(2)O逐渐取代Na_(2)O,玻璃化转变温度从537.3℃减小至514.8℃。随着Li_(2)O含量增加,有利于化学强化中的第一步交换———Li^(+)-Na^(+)交换,提高交换层深度,但会对第二步Na^(+)-K^(+)交换产生抑制作用,导致K^(+)的交换深度减小。维氏压痕测试表明化学强化可以明显地提高Na-Li-x玻璃的硬度和抗裂性。随着Li_(2)O取代Na_(2)O,化学强化后玻璃的抗裂性先增后减,在Li_(2)O摩尔分数为10%时达到极值,为72.3 N,相比Li_(2)O摩尔分数为5%时的值提升了69.3%,引入适量的Li_(2)O会提高玻璃的耐径向开裂能力。

Ni nanoparticles as electron-transfer mediators and NiS_x as interfacial active sites for coordinative enhancement of H_2-evolution performance of TiO_2

The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.

Effects of crystallinity, {001}/{101} ratio, and Au decoration on the photocatalytic activity of anatase TiO_2 crystals

Anatase TiO2 nanocrystals and sub-microcrystals with truncated octahedral bipyramidal morphologies were prepared by direct calcination of TiOF2 precursors. The as-prepared TiO2 samples were thoroughly characterized by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and UV-visible diffuse spectroscopy. It was found that the crystallinity, grain size, and {001}/{101} ratio of the samples can be increased by raising the calcination temperature from 500 to 800℃. The higher crystallinity and {001}/{101} facet ratio resulted in an increase in both aqueous and gas-phase photocatalytic activities, by inhibiting the recombination and separation of electrons and holes. After selecting two TiO2 samples with high crystallinity and {001}/{101} ratio, Au nanoparticles were decorated on their surfaces, and the photocatalytic activity of the resulting samples under visible light illumination was studied. It was found that the visible light-induced photocatalytic activity increased by 2.6 and 4.8 times, respectively, upon Au decoration of the samples prepared by calcination of TiOF2 at 700 and 800℃.

Sulfur-mediated photodeposition synthesis of NiS cocatalyst for boosting H2-evolution performance of g-C3N4 photocatalyst

Modification of nickel sulfide cocatalysts is considered to be a promising approach for efficient enhancement of the photocatalytic hydrogen production performance of g-C3N4.Providing more NiS cocatalyst to function as active sites of g-C3N4 is still highly desirable.To realize this goal,in this work,a facile sulfur-mediated photodeposition approach was developed.Specifically,photogenerated electrons excited by visible light reduce the S molecules absorbed on g-C3N4 surface to S^2‒,and subsequently NiS cocatalyst is formed in situ on the g-C3N4 surface by a combination of Ni2+and S2‒due to their small solubility product constant(Ksp=3.2×10^‒19).This approach has several advantages.The NiS cocatalyst is clearly in situ deposited on the photogenerated electron transfer sites of g-C3N4,and thus provides more active sites for H2 production.In addition,this method utilizes solar energy with mild reaction conditions at room temperature.Consequently,the synthesized NiS/g-C3N4 photocatalyst achieves excellent hydrogen generation performance with the performance of the optimal sample(244μmol h^‒1 g^‒1)close to that of 1 wt%Pt/g-C3N4(316μmol h^‒1 g^‒1,a well-known excellent photocatalyst).More importantly,the present sulfur-mediated photodeposition route is versatile and facile and can be used to deposit various metal sulfides such as CoSx,CuSx and AgSx on the g-C3N4 surface,and all the resulting metal sulfide-modified g-C3N4 photocatalysts exhibit improved H2-production performance.Our study offers a novel insight for the synthesis of high-efficiency photocatalysts.

Performance enhancement mechanism of Mn-based catalysts prepared under N_2 for NO_x removal:Evidence of the poor crystallization and oxidation of MnO_x

Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low‐temperature denitrification activity,mainly originating from multi‐valence of Mn.Most studies suggest that the catalytic activity of multi‐component oxides is superior to that of single‐component catalysts owing to the synergistic effect among the metallic elements in such materials,of which more attentions have been given to Ce as an additive owing to its powerful oxygen storage capacity,redox ability and its ready availability.As the core of SCR technology,the research points in catalyst development at the present stage of all researchers in countries mainly centralize on the optimization of active components,carriers,calcination temperature,calcination time and temperature‐raising procedure,giving little thought to the effects of the calcination atmosphere.In the present work,Ce‐modified Mn‐based catalysts were prepared by a simple impregnation method.The effects of the calcination atmosphere(N2,air or O2)on the performance of the resulting materials during NH3‐SCR and its causes of the differences were subsequently investigated and characterized using various analytical methods.Data obtained from X‐ray diffraction,thermogravimetry and temperature‐programmed reduction with hydrogen show that calcination under N2reduces both the degree of oxidation and crystallization of the MnOx.Scanning electron microscopy also demonstrates that the use of N2inhibits the growth of grains and increases the dispersion of the catalysts.In addition,the results of temperature‐programmed desorption with ammonia indicate that catalysts calcined under N2exhibit a greater quantity of acid sites.Finally,X‐ray photoelectron spectrometry and activity results demonstrate that MnOx in the lower valence states is more favorable for NH3‐SCR reactions.In conclusion,catalysts calcined under N2show superior performance during NH3‐SCR for NOx removal,allowing NO conversions up to94%at473K.

Effects of surface physicochemical properties on NH_3-SCR activity of MnO_2 catalysts with different crystal structures

α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decreased in the order:γ‐MnO2>α‐MnO2>δ‐MnO2>β‐MnO2.The NOx conversion with the use ofγ‐MnO2andα‐MnO2catalysts reached90%in the temperature range of140–200°C,while that based onβ‐MnO2reached only40%at200°C.Theγ‐MnO2andα‐MnO2nanowire crystal morphologies enabled good dispersion of the catalysts and resulted in a relatively high specific surface area.We found thatγ‐MnO2andα‐MnO2possessed stronger reducing abilities and more and stronger acidic sites than the other catalysts.In addition,more chemisorbed oxygen existed on the surface of theγ‐MnO2andα‐MnO2catalysts.Theγ‐MnO2andα‐MnO2catalysts showed excellent performance in the low‐temperature SCR of NO to N2with NH3.

Charge transfer and orbital reconstruction of non‐noble transition metal single‐atoms anchored on Ti_(2)CT_(x)‐MXenes for highly selective CO_(2) electrochemical reduction

Inspired by MXene nanosheets and their regulation of surface functional groups,a series of Ti_(2)C‐based single‐atom electrocatalysts(TM@Ti_(2)CT_(x),TM=V,Cr,Mn,Fe,Co,and Ni)with two dif‐ferent functional groups(T=–O and–S)was designed.The CO_(2)RR catalytic performance was stud‐ied using well‐defined ab initio calculations.Our results show that the CO_(2) molecule can be more readily activated on TM@Ti_(2)CO_(2) than the TM@Ti_(2)CS_(2) surface.Bader charge analysis reveals that the Ti_(2)CO_(2) substrate is involved in the adsorption reaction,and enough electrons are injected into the 2π*u orbital of CO_(2),leading to a V‐shaped CO_(2) molecular configuration and partial negative charge distribution.The V‐shaped CO_(2) further reduces the difficulty of the first hydrogenation reac‐tion step.The calculatedΔG of the first hydrogenation reaction on TM@Ti_(2)CO_(2) was significantly lower than that of the TM@Ti_(2)CS_(2) counterpart.However,the subsequent CO_(2) reduction pathways show that the UL of the potential determining step on TM@Ti_(2)CS_(2) is smaller than that of TM@Ti_(2)CO_(2).Combining the advantages of both TM@Ti_(2)CS_(2) and TM@Ti_(2)CO_(2),we designed a mixed functional group surface with–O and–S to anchor TM atoms.The results show that Cr atoms an‐chored on the surface of mixed functional groups exhibit high catalytic activity for the selective production of CH4.This study opens an exciting new avenue for the rational design of highly selec‐tive MXene‐based single‐atom CO_(2)RR electrocatalysts.

Selective adsorption of thiocyanate anions on Ag-modified g-C_3N_4 for enhanced photocatalytic hydrogen evolution

Silver‐modified semiconductor photocatalysts typically exhibit enhanced photocatalytic activitytoward the degradation of organic substances.In comparison,their hydrogen‐evolution rates arerelatively low owing to poor interfacial catalytic reactions to producing hydrogen.In the presentstudy,thiocyanate anions(SCN–)as interfacial catalytic active sites were selectively adsorbed ontothe Ag surface of g‐C3N4/Ag photocatalyst to promote interfacial H2‐evolution reactions.The thiocyanate‐modified g‐C3N4/Ag(g‐C3N4/Ag‐SCN)photocatalysts were synthesized via photodepositionof metallic Ag on g‐C3N4and subsequent selective adsorption of SCN– ions on the Ag surface by animpregnation method.The resulting g‐C3N4/Ag‐SCN photocatalysts exhibited considerably higherphotocatalytic H2‐evolution activity than the g‐C3N4,g‐C3N4/Ag,and g‐C3N4/SCN photocatalysts.Furthermore,the g‐C3N4/Ag‐SCN photocatalyst displayed the highest H2‐evolution rate(3.9μmolh?1)when the concentration of the SCN– ions was adjusted to0.3mmol L?1.The H2‐evolution rateobtained was higher than those of g‐C3N4(0.15μmol h?1)and g‐C3N4/Ag(0.71μmol h?1).Consideringthe enhanced performance of g‐C3N4/Ag upon minimal addition of SCN– ions,a synergistic effectof metallic Ag and SCN– ions is proposed―the Ag nanoparticles act as an effective electron‐transfermediator for the steady capture and rapid transportation of photogenerated electrons,while theadsorbed SCN– ions serve as an interfacial active site to effectively absorb protons from solution andpromote rapid interfacial H2‐evolution reactions.Considering the present facile synthesis and itshigh efficacy,the present work may provide new insights into preparing high‐performance photocatalytic materials

Fabrication of Z-scheme MoO3/Bi2O4 heterojunction photocatalyst with enhanced photocatalytic performance under visible light irradiation

Constructing Z-scheme heterojunction to improve the separation efficiency of photogenerated carriers of photocatalysts has gained extensive attention.In this work,we fabricated a novel Z-scheme MoO3/Bi2O4 heterojunction photocatalyst by a hydrothermal method.XPS analysis results indicated that strong interaction between MoO3 and Bi2O4 is generated,which contributes to charge transfer and separation of the photogenerated carriers.This was confirmed by photoluminescence(PL)and electrochemical impedance spectroscopy(EIS)tests.The photocatalytic performance of the as-synthesized photocatalysts was evaluated by degrading rhodamine B(RhB)in aqueous solution under visible light irradiation,showing that 15%MoO3/Bi2O4(15-MB)composite exhibited the highest photocatalytic activity,which is 2 times higher than that of Bi2O4.Besides,the heterojunction photocatalyst can keep good photocatalytic activity and stability after five recycles.Trapping experiments demonstrated that the dominant active radicals in photocatalytic reactions are superoxide radical( O2-)and holes(h+),indicating that the 15-MB composite is a Z-scheme photocatalyst.Finally,the mechanism of the Z-scheme MoO3/Bi2O4 composite for photo-degrading RhB in aqueous solution is proposed.This work provides a promising strategy for designing Bi-based Z-scheme heterojunction photocatalysts for highly efficient removal of environmental pollutants.

Highly efficient UV-visible-infrared photothermocatalytic removal of ethyl acetate over a nanocomposite of CeO_(2) and Ce-doped manganese oxide

A unique nanocomposite of CeO_(2)nanoparticles and Ce-doped manganese oxide nanofibers having a crystalline cryptomelane-type octahedral molecular sieve(KMn_(8)O_(16)·nH_(2)O,abbreviated as OMS-2)structure(denoted CeO_(2)-CeOMS-2)was prepared by the reaction of Ce(NO_(3))3 and KMnO_(4)at 90°C.CeO_(2)-CeOMS-2 shows extremely high photothermocatalytic activity,very low selectivity for acetaldehyde(an unfavorable byproduct),and excellent durability for ethyl acetate removal under UV-visible-infrared(UV-vis-IR)irradiation.In striking contrast,pure CeO_(2),pure OMS-2,and TiO_(2)(P25)showed much lower photothermocatalytic activities and higher selectivities for acetaldehyde.The CO_(2)production rate within the first five minutes(r CO2)of reaction with CeO_(2)-CeOMS-2 was as high as 1102.5μmol g-1 min-1,which is 137,17,and 30-times higher than those of pure CeO_(2),pure OMS-2,and TiO_(2)(P25),respectively.CeO_(2)-CeOMS-2 also shows good photothermocatalytic activity under vis-IR(λ>420 or 560 nm)irradiation.Further,even under vis-IR(λ>830 nm)irradiation,efficient photothermocatalytic activity was achieved.In addition,the catalytic activity of CeO_(2)-CeOMS-2 is far superior to those of pure CeO_(2)and OMS-2,which is attributed to the fact that Ce doping significantly improves the lattice oxygen activity of OMS-2.The high photothermocatalytic activity of CeO_(2)-CeOMS-2 arises from the synergy between the photocatalytic effect of the CeO_(2)nanoparticles and light-driven thermocatalysis of the Ce-doped OMS-2.The novel photoactivation of Ce-doped OMS-2,which is unlike that of conventional photocatalysis on semiconductor photocatalysts,further promotes the catalytic activity because the surface oxygen activity of Ce-doped OMS-2 is promoted upon UV-vis-IR or vis-IR(λ>560 nm)irradiation.

Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation

Copper based catalysts have high potential for the substituent of noble-metal based catalysts as their high selectivity and moderate activity for selective hydrogenation reaction;however,achieving further high catalytic stability is very difficult.In this work,the carbonization process of Cu-based organic frameworks was explored for the synthesis of highly-dispersed Cu supported by hierarchically porous carbon with high catalytic performance for selective hydrogenation of 1,3-butadiene.The porous hierarchy of carbon support and the dispersion of copper nanoparticles can be precisely tuned by controlling the carbonization process.The resultant catalyst carbonized at 600°C exhibits a rather low reaction temperature at 75°C for 100%butadiene conversion with 100%selectivity to butenes,due to its reasonable porous hierarchy and highly-dispersed copper sites.More importantly,unprecedentedly stability of the corresponding Cu catalyst was firstly observed for selective 1,3-butadiene hydrogenation,with both 100%butadiene conversion and 100%butenes selectivity over 120 h of reaction at 75°C.This study verifies that a simply control the carbonization process of metal organic frameworks can be an effective way to obtain Cu-based catalysts with superior catalytic performance for selective hydrogenation reaction.

All-organic covalent organic frameworks/perylene diimide urea polymer S-scheme photocatalyst for boosted H_(2) generation

Conjugated covalent organic frameworks(COFs)hold great promise in photocatalytic hydrogen evolution owing to their high crystallinity,large surface area,and distinct structure.However,COFs exhibit poor charge separation.Therefore,investigating highly effective COF-based photocatalysts is crucial.For the first time,conjugated COF/perylene diimide urea polymer(PUP)all-organic heterostructure with S-scheme interfacial charge-transfer channels was successfully developed and manufactured via in situ coupling of the two-dimensional triazine-based imine-linked COF(denoted as TATF-COF)with PUP.The optimal photocatalytic hydrogen-evolution rate of 94.5 mmol h^(-1) g^(-1) for TATF-COF/PUP is 3.5 times that of pure TATF-COF and is comparable to or even higher than that of the previously reported COF-based photocatalysts,resulting in an apparent quantum efficiency of up to 19.7%at 420 nm.The improved directional S-scheme charge transfer driven by the tuned built-in electric field and enhanced oxidation and reduction reaction rates of the photogenerated carriers contribute synergistically to the boosted photocatalytic H_(2) evolution.Experiments and theoretical studies reveal plausible H_(2) evolution and spatial S-scheme charge-separation mechanisms under visible-light irradiation.This study provides advanced methods for constructing all-organic S-scheme high-efficiency photocatalysts by the modulation of band structures.

Novel core‐shell Ag@AgSe_(x)nanoparticle co‐catalyst:In situ surface selenization for efficient photocatalytic H_(2)production of TiO_(2)

Effective charge separation and rapid interfacial H_(2) production are imperative for the construction of efficient photocatalysts.Compared to Pt,the metallic Ag co‐catalyst with its strong electron‐trapping ability and excellent electronic conductivity typically exhibits an extremely limited photocatalytic H_(2-)evolution rate owing to its sluggish interfacial H_(2)‐generation reaction.In this study,amorphous AgSe_(x) was incorporated in situ onto metallic Ag as a novel and excellent H_(2)‐evolution active site to boost the interfacial H_(2)‐generation rate of Ag nanoparticles in a TiO_(2)/Ag system.Core‐shell Ag@AgSe_(x)nanoparticle‐modified TiO_(2)photocatalysts were prepared via a two‐step pathway involving the photodeposition of metallic Ag and the selective surface selenization of metallic Ag to yield amorphous AgSe_(x)shells.The as‐prepared TiO_(2)/Ag@AgSe_(x)(20μL)photocatalyst exhibited an excellent H_(2‐)production performance of 853.0μmol h^(-1)g^(-1),prominently outperforming the TiO_(2)and TiO_(2)/Ag samples by factors of 11.6 and 2.4,respectively.Experimental investigations and DFT calculations revealed that the enhanced H_(2‐)generation activity of the TiO_(2)/Ag@AgSe_(x)photocatalyst could be accounted by synergistic interactions of the Ag@AgSe_(x)co‐catalyst.Essentially,the metallic Ag core could quickly capture and transport the photoinduced electrons from TiO_(2)to the amorphous AgSe_(x)shell,whereas the amorphous AgSe_(x)shell provided large active sites for boosting the interfacial H_(2)evolution.This study offers a facile route for the construction of novel core‐shell co‐catalysts for sustainable H_(2)evolution.

太阳能吸热器用莫来石--碳化硅陶瓷的原位合成(英文)

采用半干压成型和无压烧成技术,原位合成了用于太阳能热发电吸热器的莫来石结合碳化硅（SiC）吸热陶瓷。研究结果表明：经1 520℃烧成的样品B2（粒径≤61μm SiC 72%,粒径≤20μm SiC 18%,工业氧化铝4.64%,苏州高岭土5.36%）的综合性能最佳,其显气孔率、吸水率、体积密度和抗折强度分别为28.40%、13.35%、2.13g/cm^3和44.20MPa;热震试验30次（1 100℃~室温,风冷）,样品无裂纹,强度增加率达52.30%;在1 300℃氧化100h后,样品的氧化增重为25.43mg/cm^2,氧化动力学常数为1.80×10^-7kg^2/（m4·s）。物相分析表明,样品的相组成为碳化硅、莫来石、石英和刚玉。显微结构分析表明,原位合成的莫来石结合于碳化硅颗粒间,赋予样品较好的抗折强度。热震试验30次后,可在样品中观察到更加致密的结构,碳化硅晶粒被树枝状微晶紧密联接,改善了样品的抗热震性。莫来石--碳化硅复相陶瓷可作为塔式太阳能热发电吸热器的潜在应用材料。