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.

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.

“Zero‑Strain” NiNb_(2)O_(6) Fibers for All‑Climate Lithium Storage

Niobates are promising all-climate Li^(+)-storage anode material due to their fast charge transport,large specific capacities,and resistance to electrolyte reaction.However,their moderate unit-cellvolume expansion(generally 5%–10%)during Li^(+)storage causes unsatisfactory long-term cyclability.Here,“zero-strain”NiNb_(2)O_(6) fibers are explored as a new anode material with comprehensively good electrochemical properties.During Li^(+)storage,the expansion of electrochemical inactive NiO_(6) octahedra almost fully offsets the shrinkage of active NbO_(6) octahedra through reversible O movement.Such superior volume-accommodation capability of the NiO_(6) layers guarantees the“zero-strain”behavior of NiNb_(2)O_(6) in a broad temperature range(0.53%//0.51%//0.74%at 25//−10//60℃),leading to the excellent cyclability of the NiNb_(2)O_(6) fibers(92.8%//99.2%//91.1%capacity retention after 1000//2000//1000 cycles at 10C and 25//−10//60℃).This NiNb_(2)O_(6) material further exhibits a large reversible capacity(300//184//318 mAh g−1 at 0.1C and 25//−10//60℃)and outstanding rate performance(10 to 0.5C capacity percentage of 64.3%//50.0%//65.4%at 25//−10//60℃).Therefore,the NiNb_(2)O_(6) fibers are especially suitable for large-capacity,fast-charging,long-life,and all-climate lithium-ion batteries.

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.

含碳纳米C-TiO2薄膜光催化降解气相甲苯研究

对以工业丙烷为燃料、空气为氧化剂、TiCl4为先驱物的火焰CVD法制备的含碳纳米C-TiO2光催化剂,用沉降法在石英玻璃管内壁制备C-TiO2纳米薄膜,以管式反应器为光催化氧化装置,实验研究了含碳纳米C-TiO2的纳米薄膜对甲苯气体的光催化降解规律。探讨了甲苯初始浓度和相对湿度等因素对降解率的影响。实验结果表明,相对湿度约为60%时,对甲苯有最佳的光催化降解效果。在催化剂负载量约为4.9mg、主波长为254nm和365nm的8W紫外灯各一盏、甲苯初始浓度约为60mg/m3、气体流量为400mL/min(甲苯在光催化器中停留时间约为3.45s)的条件下,甲苯的降解率可达45%。

C-TiO_2复合催化剂的制备及其表征

以大孔-介孔炭材料为催化剂载体,用溶胶-凝胶法合成制备复合光催化剂C-TiO2,并分别用X射线衍射(XRD)、透射电子显微镜(TEM)、UV-Vis漫反射光谱(DRS)对其物性进行表征;采用该复合催化剂降解甲基橙溶液评价其光催化效果.结果表明:C-TiO2复合材料不是简单的物理负载,而是在合成制备及高温煅烧后,在载体与催化剂的界面处发生了化学键合;与P25-TiO2相比,该复合催化剂催化效果显著提高.

Low temperature molten salt synthesis of porous La_(1-x)Sr_xMn_(0.8)Fe_(0.2)O_3(0≤x≤0.6) microspheres with high catalytic activity for CO oxidation

A molten salt method was developed to prepare porous La1‐xSrxMn0.8Fe0.2O3 （0≤ x ≤ 0.6） micro‐spheres using hierarchical porous δ‐MnO2 microspheres as a template in eutectic NaNO3‐KNO3. X‐ray diffraction patterns showed that single phase LaMn0.8Fe0.2O3 with good crystallinity was syn‐thesized at 450℃ after 4 h. Transmission electron microscope images exhibited that the LaMn0.8Fe0.2O3 sample obtained at 450？？ after 4 h possessed a porous spherical morphology com‐posed of aggregated nanocrystallites. Field emission scanning electron microscope images indicated that the growth of the porous LaMn0.8Fe0.2O3 microspheres has two stages. SEM pictures showed that a higher calcination temperature than 450？？ had an adverse effect on the formation of a po‐rous spherical structure. The LaMn0.8Fe0.2O3 sample obtained at 450？？ after 4 h displayed a high BET surface area of 55.73 m2/g with a pore size of 9.38 nm. Fourier transform infrared spectra suggested that Sr2＋ions entered the A sites and induced a decrease of the binding energy between Mn and O. The CO conversion with the La1‐xSrxMn0.8Fe0.2O3 （0≤x≤0.6） samples indicated that the La0.4Sr0.6Mn0.8Fe0.2O3 sample had the best catalytic activity and stability. Further analysis by X‐ray photoelectron spectroscopy demonstrated that Sr2＋doping altered the content of Mn4＋ions, oxygen vacancies and adsorbed oxygen species on the surface, which affected the catalytic performance for CO oxidation.

多孔C-TiO2复合材料的制备及光催化性能研究

利用廉价易得的油菜花粉作为碳基材料的原料,得到多孔的碳基质,在其表面负载二氧化钛,制备出不同二氧化钛负载量的C-TiO2复合材料。利用X射线衍射、扫描电子显微镜、N2吸附-脱附等表征手段对材料的形貌进行了表征。以光催化降解甲基橙为有机污染物降解模型,对该复合材料的光催化性能进行了评估。结果表明:碳和二氧化钛的共同作用,极大地提高了水中甲基橙的降解率;制备的CT3复合材料对甲基橙具有优异、稳定的光催化降解性能,对甲基橙的降解率达到92%,在处理有机污染物方面有广阔的应用前景。

A Novel Technology for Post-Treating of Porous Silicon Thick Films in H_2O_2

The solution of H 2O 2 is proposed to post-treat thick porous silicon (PS) films.The prepared PS film as the cathode is applied about 10mA/cm 2 current in mixture of ethanol,HF,and H 2O 2 solutions,which is expected to improve the stability and the smoothness of the surface and the mechanical property of the thick porous silicon films.The microstructure of the PS thick films with thicknesse of 20μm and 70μm has been studied.The SEM images show significant improved smoothness on surface of PS films,and XRD spectra suggest the formation of oxide layer after post-treating in H 2O 2.

一种应用于车位监视系统的梭状C-TiO_2@Co_3O_4锂离子电池性能研究

针对共享车位监视系统备用电池的需求,提出了一种新型的锂离子电池负极材料的制备方法。以TiO_2纳米纺锤作为基体材料,制备了C-TiO_2@Co_3O_4纳米复合物,循环100周后可逆容量保持450m Ah/g仍远高于商业化碳材料,首次放电容量和充电容量分别为930和722 mAh/g,对应库伦效率为77.6%。优异的性能决定其可应用于车位监视系统备用电池的制造。

C-TiO_2/Ti-Cu_2O/Cu光催化燃料电池的性能

采用溶胶-凝胶法制备了C-TiO_2/Ti膜电极,其X-射线衍射(XRD)结果表明,C掺杂有效抑制了TiO_2催化剂由锐钛矿相向金红石相的转变.以C-TiO_2/Ti作为光催化燃料电池(PFC)的阳极,Cu_2O/Cu为阴极,考察了C-TiO_2/Ti的制备条件和染料初始浓度及p H值对PFC性能的影响,得到PFC的最佳性能:短路电流密度为0.084 m A·cm^(-2),开路电压为0.385 V,最大输出功率密度为5.91×10^(-3)m W·cm^(-2),填充因子(FF)为0.18,光催化处理20 mg·L^(-1)罗丹明B染料废水90 min,脱色率达到91.7%.处理过程中罗丹明B溶液的紫外-可见分光光谱表明,可见光区最大吸收波长略有蓝移,可见和紫外光区的光吸收均下降,说明分子遭到了破坏,并发生了矿化.

一步合成核壳结构C-TiO_2复合材料及UV-Vis光催化降解染料

以二(乙酰丙酮基)钛酸二异丙酯,异丙醇和尿素为原料,通过简单的一步无模板溶剂热法合成了核壳结构C-TiO_2复合材料前驱体,随后在氩气条件下不同温度煅烧得到高晶相CTiO_2复合材料。运用SEM、TEM、XRD、XPS、Raman、TG、N_2吸附-脱附、UV-Vis漫反射等技术对样品进行表征、并在UV-Vis光照射下分别对Rh B、MB、CR 3种染料溶液进行了催化降解测试。结果表明:550℃煅烧的样品的催化性能最佳,其为高晶相的锐钛矿相TiO_2材料,并包含少量的碳,而且550℃煅烧的样品依然保持了核壳结构。比表面积能够达到85.69 m^2/g、孔直径为16.4 nm、孔体积为0.423 m^3/g。其优越的催化性能可归于较大的比表面积能够提供吸附更多的染料分子;核壳结构更有利于捕获更多的光量子;高晶相更有利于催化过程中电子-空穴对的分离。

Porous TiO2-coated Magnetic Core-Shell Nanocomposites：Preparation and Enhanced Photocatalytic Activity

The core-shell structured TiO2/SiO2 @Fe3O4 photocatalysts were prepared using Fe3O4 as magnetic core,tetraethoxysilane（TEOS） as silica source and tetrabutyl titanate（TBOT） as titanium sources.The as-obtained structure was composed of a SiO2@Fe3O4 core and a porous TiO2 shell.The diameter of SiO2@Fe3O4 core was about 205 nm with thickness of porous TiO2 of about 5-6 nm.The 9%TiO2/6%SiO2@Fe3O4 microspheres possess the highest BET surface area and the BJH pore volume,which are 373.5 m2.g-1 and 0.28 cm3.g-1,respectively.The 9%TiO2/6%SiO2@Fe3O4 photocatalyst exhibited an excellent performance for the degradation of methyl orange and methylene blue dyes.Two different dyes were completely decolorized in 60 min under UV irradiation.The photocatalytic activity and the amount of catalyst were almost not decrease after recycling for 6 times by using external magnetic field.

Visualization of CO_2 and oil immiscible and miscible flow processes in porous media using NMR micro-imaging

CO2 flooding is considered not only one of the most effective enhanced oil recovery （EOR） methods, but also an important alternative for geological CO2 storage. In this paper, the visualization of CO2 flooding was studied using a 400 MHz NMR micro-imaging system. For gaseous CO2 immiscible displacement, it was found that CO2 channeling or fingering occurred due to the difference of fluid viscosity and density. Thus, the sweep efficiency was small and the final residual oil saturation was 53.1%. For supercritical CO2 miscible displacement, the results showed that piston-like displacement occurred, viscous fingering and the gravity override caused by the low viscosity and density of the gas was effectively restrained, and the velocity of CO2 front was uniform. The sweep efficiency was so high that the final residual oil saturation was 33.9%, which indicated CO2 miscible displacement could enhance oil recovery more than CO2 immiscible displacement. In addition, the average velocity of CO2 front was evaluated through analyzing the oil saturation profile. A special core analysis method has been applied to in-situ oil saturation data to directly evaluate the local Darcy phase velocities and capillary dispersion rate.

Surface functionalized N-C-TiO_(2)/C nanocomposites derived from metal-organic framework in water vapour for enhanced photocatalytic H generation

Surface-functionalized nitrogen/carbon co-doped polymorphic TiO_(2) phase junction nanoparticles uniformly distributed in porous carbon matrix were synthesized by a simple one-step pyrolysis of titanium based metal-organic framework(MOF),NH_(2)-MIL^(-1)25(Ti) at 700℃ under water vapour atmosphere.Introducing water vapour during the pyrolysis of NH_(2)-MIL^(-1)25(Ti) not only functionalizes the derived porous carbon matrix with carboxyl groups but also forms additional oxygen-rich N like interstitial/intraband states lying above the valence band of TiO2 along with the self-doped carbo n,which further narrows the energy band gaps of polymorphic TiO2 nanoparticles that enhance photocatalytic charge transfer efficiency.Without co-catalyst,sample N-C-TiO2/CArW demonstrates H_(2) evolution activity of 426 μmol gcat-1h^(-1),which remarkably outperforms commercial TiO_(2)(P-25) and N-C-TiO_(2)/CAr with a 5-fold and 3-fold H_(2) generation,respectively.This study clearly shows that water vapour atmosphere during the pyrolysis increases the hydrophilicity of the Ti-MOF derived composites by functionalizing porous carbon matrix with carboxylic groups,as well as enhancing the electrical conductivity and charge transfer efficiency due to the formation of additional localized oxygen-rich N like interstitial/intraband states.This work also demonstrates that by optimizing the anatase-rutile phase composition of the TiO2 polymorphs,tuning the energy band gaps by N/C co-doping and functionalizing the porous carbon matrix in the N-C-TiO2/C nanocomposites,the photocatalytic H_(2) generation activity can be further enhanced.