Hollow Porous SiO_2 Nanocubes with Enhanced Lithium Storage Properties

The high theoretical capacity and low discharge potential of silicon have attracted much attention on Si-based anodes. Herein, hollow porous SiO2 nanocubes have been prepared via a two-step hard-template process and evaluated as electrode materials for lithium-ion batteries. The hollow porous SiO2 nanocubes exhibited a reversible capacity of 919 mAh/g over 30 cycles. The excellent property could be attributed to the unique hollow nanostructure with large volume interior and numerous crevices in the shell, which could accommodate the volume change and alleviate the structural strain during Li ions insertion and extraction, as well as allow rapid access of Li ions during charge/discharge cycling. It is found that the formation of irreversible or reversible lithium silicates in the anodes determines the capacity of a deep-cycle battery, fast transportation of Li ions in hollow porous SiO2 nanocubes is preferred to form Li2O and Si, contributing to the high reversible capacity. The hollow porous SiO2 nanocubes have great potential applications for Li-ion batteries due to their remarkable electrochemical performance and low cost.

Lignite-Based Hierarchical Porous C/SiO_(x)Composites as High-Performance Anode for Potassium-Ion Batteries

Silicon oxide(SiO_(x),0<x≤2)has been recognized as a prominent anode material in lithium-ion batteries and sodium-ion batteries due to its high theoretical capacity,suitable electrochemical potential,and earth abundance.However,it is intrinsically poor electronic conductivity and excessive volume expansion during potassiation/depotassiation process hinder its application in potassium-ion batteries.Herein,we reported a hierarchical porous C/SiO_(x)potassium-ion batteries anode using lignite as raw material via a one-step carbonization and activation method.The amorphous C skeleton around SiO_(x)particles can effectively buffer the volume expansion,and improve the ionic/electronic conductivity and structural integrity,achieving outstanding rate capability and cyclability.As expected,the obtained C/SiO_(x)composite delivers a superb specific capacity of 370 mAh g^(-1)at 0.1 A g^(-1)after 100 cycles as well as a highly reversible capacity of 208 mAh g^(-1)after 1200 cycles at 1.0 A g^(-1).Moreover,the potassium ion storage mechanism of C/SiO_(x)electrodes was investigated by ex-situ X-ray diffraction and transmission electron microscopy,revealing the formation of reversible products of K_(6.8)Si_(45.3)and K_(4)SiO_(4),accompanied by generation of irreversible K2O after the first cycle.This work sheds light on designing low-cost Si-based anode materials for high-performance potassium-ion batteries and beyond.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

A Method for Preparation of Ordered Porous Silicon Based on a 2D SiO_2 Template

A new method for fabricating ordered porous silicon is reported. A two-dimensional silica nanosphere array is used as a template with a hydrofluoric acid-hydrogen peroxide solution for etching the nanospheres. The initial diameter and distribution of the holes in the resulting porous silicon layer are determined by the size and distribution of the silica nanospheres. The corrosion time can be used to control the depths of the holes. It is found that the presence of a SiO2 layer, formed by the oxidation of the rough internal surface of the hole, is the primary reason allowing the corrosion to proceed. Ultraviolet reflection and thermal conductivity measurements show that the diameter and distribution of the holes have a great influence on properties of the porous silicon.

Identification of pore size in porous SiO_2 thin film by positron annihilation

Positron annihilation lifetime and Doppler broadening of annihilation line techniques have been used to obtain information about the small pore structure and size of porous SiO2 thin film produced by sputtered Al-Si thin film and etched Al-Si thin film. The film is prepared by an Al/Si 75：25 at.-% （A175Si25） target with the radiofrequency （RF） power of 66 W at room temperature. A 5 wt.-% phosphoric acid solution is used to etch the Al cylinders. All the A1 cylinders dissolved in the solution after 15 h at room temperature, and the sample is subsequently rinsed in pure water. In this way, the porous SiO2 on the Si substrate is produced. From our results, the values of all lifetime components in the spectra of Al-Si thin film are less than 1 ns, but the value of one of the lifetime components in the spectra of porous SiO2 thin film is τ = 7.80 ns. With these values of lifetime, RTE （Rectangular Pore Extension） model has been used to analyze the pore size.

Preparation,characterization and catalytic behavior of hierachically porous CuO/α-Fe_2O_3/SiO_2 composite material for CO and o-DCB oxidation

Hierachically porous （HP） CuO/α-Fe2O3/SiO2 composite material was fabricated by sol-gel method and multi-hydrothermal processes using HP-SiO2 as support.The resulting material was characterized by N2 adsorption-desorption,X-ray diffraction and scanning electron microscopy.The as-prepared CuO/Fe2O3/HP-SiO2 sample,with α-Fe2O3 and CuO nanocrystals,possessed a co-continuous skeleton,through-macroporous and mesoporous structure.Its catalytic behavior for CO and o-DCB oxidation was investigated.The result showed that CuO/Fe2O3/HP-SiO2 catalyst exhibited high catalytic activity for both CO and o-DCB oxidation,indicating its potential application in combined abatement of CO and chlorinated volatile organic compounds.

Evolution of the porous structure for phosphoric acid etching carbon as cathodes in Li–O_(2) batteries:Pyrolysis temperature-induced characteristics changes

Although biomass-derived carbon(biochar)has been widely used in the energy field,the relation between the carbonization condition and the physical/chemical property of the product remains elusive.Here,we revealed the carbonization condition's effect on the morphology,surface property,and electrochemical performance of the obtained carbon.An open slit pore structure with shower-puff-like nanoparticles can be obtained by finely tuning the carbonization temperature,and its unique pore structure and surface properties enable the Li–O_(2) battery with cycling longevity(221 cycles with 99.8%Coulombic efficiency at 0.2 mA cm^(−2) and controlled discharge–charge depths of 500 mAh g^(−1))and high capacity(16,334 mAh g^(−1) at 0.02 mA cm^(−2)).This work provides a greater understanding of the mechanism of the biochar carbonization procedure under various pyrolysis conditions,paving the way for future study of energy storage devices.

Porous TiFe_(2) intermetallic compound fabricated via elemental powder reactive synthesis

Porous intermetallics show potential in the field of filtration and separation as well as in the field of catalysis.Herein,porous Ti Fe2intermetallics were fabricated by the reactive synthesis of elemental powders.The phase transformation and pore formation of porous TiFe2intermetallics were investigated,and its corrosion behavior and hydrogen evolution reaction(HER)performance in alkali solution were studied.Porous TiFe2intermetallics with porosity in the range of 34.4%-56.4%were synthesized by the diffusion reaction of Ti and Fe elements,and the pore formation of porous TiFe2intermetallic compound is the result of a combination of the bridging effect and the Kirkendall effect.The porous TiFe2samples exhibit better corrosion resistance compared with porous 316L stainless steel,which is related to the formation of uniform nanosheets on the surface that hinder further corrosion,and porous TiFe2electrode shows the overpotential of 220.6 and 295.6 mV at 10 and 100 mA·cm-2,suggesting a good catalytic performance.The synthesized porous Fe-based intermetallic has a controllable pore structure as well as excellent corrosion resistance,showing its potential in the field of filtration and separation.

Formation Characteristics of CO_(2) Hydrates in the Presence of Porous Media and NaCl

Hydrate-based CO_(2) sequestration is an effective method for reducing the greenhouse effect,and the presence of porous media and NaCl can impact the formation characteristics of hydrates.This study uses the constant volume temperature search method to investigate the effects of quartz sand particle size(0.006‒0.03 mm),water saturation(30%–90%),and NaCl concentration(1%‒9%)on the phase equilibrium and kinetics of CO_(2) hydrates within a temperature range of 273‒285 K and pressure range of 1.0‒3.5 MPa.The results indicate that a decrease in quartz sand particle size or an increase in NaCl concentration shifts the hydrate phase equilibrium curve towards lower temperatures and higher pressures,making hydrate generation conditions more demanding.In different particle size systems,there are no significant changes in the rate of CO_(2) hydrate formation or conversion rate.The highest hydrate conversion rate of 71.1%is observed in a 0.015 mm particle size system.With increasing water saturation,both the generation rate and conversion rate of CO_(2) hydrates show a trend of first increasing and then decreasing.Meanwhile,low concentrations of NaCl(1%–3%)are found to enhance the formation and conversion rates of CO_(2) hydrates.However,as NaCl concentration increases,the rate of CO_(2) hydrate formation and conversion rate decrease.

MOF‐derived 1D/3D N‐doped porous carbon for spatially confined electrochemical CO_(2) reduction to adjustable syngas

Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.

Reusable salt-template strategy for synthesis of porous nitrogen-rich carbon boosts H_(2)S selective oxidation

Removing hydrogen sulfide(H_(2)S)via the selective oxidation has been considered an effective way to further purify the indusial sulfurcontaining due to it can completely transform residual H_(2)S into elemental sulfur.While N-doped porous carbon was applied to H_(2)S selective oxidation,a sustainable methodology for the synthesis of efficient and stable N-doped carbon catalysts remains a difficulty,limiting its future development in large-scale applications.Herein,we present porous,honeycomb-like N-doped carbon catalysts with large specific surface areas,high pyridinic N content,and numerous structural defects for H_(2)S selective oxidation prepared using reusable NaCl as the template.The asprepared NC-10-800 catalyst exhibits excellent catalytic performance(sulfur formation rate of 784 g_(sulfur) kg_(cat.)^(-1) h^(-1)),outstanding stability(>100 h),and excellent anti-water vapor,anti-CO_(2) and anti-oxidation properties,suggesting significant potential for practical industrial application.The characterization results and kinetic study demonstrate that the large surface areas and structural defects created by the molten salt at high temperature enhance the exposure of pyridinic N sites and thus accelerate the catalytic activity.Importantly,the water-soluble NaCl template could be easily washed from the carbon nanomaterials,and thus the downstream salt-containing wastewater could be subsequently reused for the dissolution of carbon precursors.This environment-friendly,low-cost,reusable salt-template strategy has significant implications for the development of N-doped carbon catalysts for practical applications.

基于瞬态平面热源法测定SiO_2气凝胶导热系数的试验

阐述基于瞬态平面热源法的Hot Disk热常数分析仪的测试原理,利用测试标准304不锈钢对仪器准确性及重复性进行了验证,同时研究了不同孔隙率SiO_2气凝胶的导热系数随温度和压力变化的特点。结果表明:Hot Disk热常数分析仪在测试SiO_2气凝胶导热系数方面具有优异的准确性和重复性;在相同的温度和压力下,SiO_2气凝胶的导热系数随着孔隙率增大而变小;当环境压力小于5×10~3 Pa时,导热系数随环境压力改变而变化不明显,当环境压力大于5×10~3 Pa,导热系数随环境压力升高而变化较大;当环境温度在100~500℃范围内,SiO_2气凝胶的导热系数随环境温度升高而略微变大,当环境温度继续升高时,导热系数随环境温度升高而迅速增大。

Fabrication and photodegradation properties of TiO_2 nanotubes on porous Ti by anodization

Both Ti foil and porous Ti were anodized in 0.5%HF and in ethylene glycol electrolyte containing 0.5%NH4F(mass fraction) separately. The results show that TiO2 nanotubes can be formed on Ti foil by both processes, whereas TiO2 nanotubes can be formed on porous Ti only in the second process. The overhigh current density led to the failure of the formation nanotubes on porous Ti in 0.5%HF electrolyte. TiO2 nanotubes were characterized by SEM and XRD. TiO2 nanotubes on porous Ti were thinner than those on Ti foil. Anatase was formed when TiO2 nanotubes were annealed at 400 °C and fully turned into rutile at 700 °C. To obtain good photodegradation, the optimal heat treatment temperature of TiO2 nanotubes was 450 °C. The porosity of the substrates influenced photodegradation properties. TiO2 nanotubes on porous Ti with 60% porosity had the best photodegradation.

Ce添加对Cu-Fe/SiO_2催化合成气制低碳醇性能的影响

采用共浸渍法制备了添加不同Ce含量(相对于SiO_2的摩尔分数为0-20%)的Ce-Cu-Fe/SiO_2催化剂,在连续流动微型固定床反应器中考察了其催化CO加氢合成低碳醇反应的性能,并采用X射线衍射(XRD)、低温N_2吸附、程序升温还原(H_2-TPR)、CO吸附傅里叶变换红外光谱(CO-FTIR)和CO程序升温脱附(CO-TPD)技术对催化剂进行了表征.结果表吸:添加适量的Ce,一方面降低了Cu的晶粒大小,提高了Cu的分散度,进而提高了对CO的吸附能力;另一方面掺入的Ce和Cu之间存在相互作用,提高了CO解离和非解离吸附的能力,从而有利于CH_x的生成和CO的插入反应.上述两方面的共同作用同时提高了Cu-Fe/SiO_3催化剂的活性和醇的选择性.当Ce含量为10%时,在压力为3.0 MPa,温度为250℃,空速为6000 mL·g^(-1)·h^(-1)和H_2/CO摩尔比为2的反应条件下,Ce-Cu-Fe/SiO_2催化剂上醇的时空产率达到121.0 g·kg^(-1)·h^(-1),比未添加Ce的Cu-Fe/SiO_2催化剂的时空产率(58.0 g·kg^(-1)·h^(-1))提高了一倍以上.

SiO_2纳米多孔材料制备及其保温隔热特性研究

以正硅酸乙酯为前驱体,采用溶胶 凝胶法制备了SiO2纳米多孔材料。通过采用先酸后碱二步法催化等多种优化工序,使材料具有多孔纳米结构,气孔率和比表面积增高,孔径和热导率降低,其孔洞率最高可达95%以上,孔径约20nm,比表面积1120cm2/g,体积密度0.003g/cm3,500℃时的热导率低于0.023W·m-1·K-1,成为保温性能最佳的固态材料。探讨了相关的保温隔热机理,认为低热传导系数硅材料,当具有很高的孔洞率和很低的体积密度时能更有效地阻隔热量的固体传导和气体传导。当孔径小于红外波长时,绝热效果有本质上的突变和提高。进行了纳米多孔材料和硅酸钙及有机硅复合的研究,制备了兼有很好保温性能和机械性能的保温隔热块体和柔性薄膜。

镁合金表面SiO_2-ZrO_2溶胶凝胶膜的耐蚀性

采用溶胶-凝胶法在AZ91D镁合金表面制备SiO2-ZrO2复合溶胶凝胶膜。研究膜层制备工艺中的干燥、固化过程对膜层耐腐蚀性能的影响,从而确定了SiO2-ZrO2复合溶胶凝胶膜在镁合金表面的最佳沉积工艺。通过全浸腐蚀试验和电化学测试方法评价了膜层的耐腐蚀性能。试验确定最佳沉积工艺参数:干燥温度为80℃、干燥时间为9h、固化温度为250℃、固化时间为1h。在优化工艺条件下制备的溶胶凝胶膜层对镁合金基体有一定的防护作用,提高了镁合金的耐蚀性。

采用Ag-Cu-In-Ti钎料真空钎焊SiO_(2f)/SiO_2复合陶瓷与铌

设计了Ag-（15~26）Cu-（13~20）In-（3.1~6.9）Ti活性钎料,分别在780℃/20 min,780℃/40 min和800℃/10 min三种参数下实现了SiO_（2f）/SiO_2复合材料与铌的连接,分析了接头微观组织,测试了接头室温抗剪强度.其中800℃/10 min钎焊参数下的接头平均抗剪强度最高,达到21.6 MPa;微观分析结果表明,接头中靠近SiO_（2f）/SiO_2母材界面处形成了厚度约为2μm的连续扩散反应层,靠近铌的界面钎料与母材也形成了良好的结合.该钎焊参数下接头界面物相依次为：SiO_（2f）/SiO_2→TiO＋TiSi_2→TiO＋Cu_3Ti→Ag（s,s）＋Ag_3In＋Cu（s,s）→Nb.

纳米SiO_2改性ACQ防腐处理材的制备及抗流失性研究

利用纳米SiO_2改性ACQ防腐剂,以提高ACQ处理材的抗流失性。利用单因素法考察纳米SiO_2在ACQ溶液中的最佳分散条件,并考察改性ACQ处理材的抗流失性及其化学结构变化。结果表明:纳米SiO_2改性理想的工艺条件为:ACQ浓度为1.0%,纳米SiO_2质量为0.01 g,六偏磷酸钠/纳米SiO_2比例为15:1,超声时间为30 min,超声温度为20℃。经纳米SiO_2改性的ACQ处理材,其流失率明显下降,且从FTIR谱图中可见,纳米SiO_2改性处理是提高ACQ处理材中有效成分铜抗流失性的最主要原因。

偶联剂对EVOH/纳米SiO_2复合材料结构与性能的影响

采用不同的偶联剂KH550、KH560、KH570和KH8431对纳米SiO2进行表面改性,采用熔融共混法将未改性和改性纳米SiO2(5%(质量分数)SiO2)与EVOH共混制成复合材料,并吹塑成薄膜。利用FT-IR、TEM、SEM对不同偶联剂处理的纳米SiO2和复合材料的结构进行表征,并对复合材料的流变性能、阻隔性能、力学性能、耐热性能和透明性进行了表征。结果表明,纳米SiO2与4种偶联剂均形成化学键合,改性纳米SiO2比未改性纳米SiO2在EVOH中分散性好,加工时熔体的流动性更好。用KH550处理的纳米SiO2在EVOH中分散性最好,与EVOH能形成较大界面相互作用力,与EVOH/未改性纳米SiO2复合材料相比,EVOH/改性纳米SiO2复合材料的拉伸强度和储能模量分别提高17.2%和136%,透湿、透氧系数分别下降11.2%和9.5%,透光率达到74.9%,雾度为14.9%。