载体氧空位提升Sabatier反应钌基催化剂性能研究

通过尿素的掺杂,有效诱导Al_(2)O_(3)载体氧空位的形成,进而通过金属-载体之间的相互作用,提升Al_(2)O_(3)载体表面Ru基活性物种的分散度,调控Ru基活性中心的电子性质,从而达到有效提升Sabatier反应Ru基催化剂性能的目的。在此过程中,借助^(27)Al核磁(^(27)Al-NMR)验证了尿素的掺杂可有效诱导Al_(2)O_(3)载体中氧空位的形成。通过透射电子显微镜(TEM)发现,富含氧空位的Al_(2)O_(3)载体可将负载的Ru颗粒稳定在3.7 nm左右,且粒径分布集中。通过X射线光电子能谱(XPS)和H_(2)程序升温还原(H_(2)-TPR)发现,载体氧空位可有效调控Al_(2)O_(3)载体表面Ru基活性位点的电子性质。经过Sabatier反应性能测试发现,在300℃,n CO_(2)∶n H_(2)=1∶4,空速为6000 mL·g^(-1)·h^(-1)的反应条件下,CO_(2)转化率可达61.25%,CH_(4)选择性可达92.31%,而且,在20 h的反应时间内,催化活性没有明显衰减。

调控五配位Al^(3+)含量制备高性能低温Sabatier反应催化剂

为了制备出高性能低温Sabatier反应Ru基催化剂,通过调控Al_(2)O_(3)载体中五配位Al^(3+)的含量(五配位Al^(3+)占Al物种的比例),实现对Ru基活性位点电子性质的调控。在此过程中,利用~(27)Al固体核磁共振(~(27)Al-NMR)检测Al_(2)O_(3)载体中五配位Al^(3+)的含量,借助X射线光电子能谱仪(XPS)和H_2程序升温还原(H_(2)-TPR)考察Ru基活性位点电子性质的调控效果,利用固定床反应器测试催化剂性能。结果表明,Al_(2)O_(3)载体中的五配位Al^(3+)可有效调控Ru基活性位点的电子性质,进而提升低温Sabatier反应Ru基催化剂性能。其中,以五配位Al^(3+)含量约为28.1%的Al_(2)O_(3)载体制备的Ru基催化剂,在低温区(<300℃)的CO_(2)转化率和CH_4选择性均可达90%以上。而且,在100 h的稳定性测试中,催化性能没有明显降低。

Advances in sodium-ion batteries at low-temperature: Challenges and strategies

With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithiumion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Fu rthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in performance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mechanism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to100℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utilization of effective electrode materials and electrolyte components.Furthermore,the safety concerns associated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.

Preparation of Lead-free Base Glaze Suitable for Pearlescent Pigments by Low-temperature Solid-phase Reaction with Alkali Waste

A lead-free base glaze suitable for pearlescent pigments was prepared by a low-temperature solid-phase reaction with alkali waste.Tests were performed to evaluate the effects of the sintering conditions and alkali waste composition on the prepared base glaze and pearlescent glaze.The experimental results show that partially replacing SiO_(2) with B_(2)O_(3) effectively reduced the sintering temperature and time to form a glass network,but the network structure becomes disconnected as the B_(2)O_(3) content increases.An amorphous base glaze was obtained when soda ash was replaced with a small amount of alkali waste,but increasing the addition of NaCl further was adverse to base glaze formation by resulting in crystallization of the base glaze and a decrease in the bridging oxygen content.The pearlescent pigment was thermally stable in the glaze at 750℃,while higher temperatures caused the crystalline phase of NaAlSiO_(4) to appear and adhere to the surface of pigment granules,which degraded the pearlescent effect of the glaze.

Sabatier反应器的小型化研究

针对中长期载人航天CO2处理与02循环再生问题,在Sabatier反应热力学分析的基础上,通过优化反应器高低温区的反应温度及进出口温度并预测冷却气体的最佳流量及出口温度,提出了适于载人航天的Sabatier反应流程及基于微化工技术的微反应器设计方案,制造出一套地面Sabatier反应试验样机.在H2/CO2摩尔比为3.5、原料气流量为4.3L/min、高温反应器温度为260-268℃、低温反应器温度为210-235℃的条件下,头现了4500小时稳定运行、耳转化率大于98%、系统压力降小于4kPa的结果,为未来实用微反应器的设计奠定了技术基础.

Sabatier化学反应热特性仿真研究

目的借鉴前人的实验研究工作,采用比表面积拟合的方法对Sabatier化学反应的热特性进行验证计算,从而证明方法的合理性与可行性。方法文章采用质量作用定律与Arrhenius公式建立表面化学过程,并分两部分进行计算:第一部分通过比较热化学特性的计算值与实验数据,提出需要采用拟合法的必要性;第二部分采用不同比表面积模型进行化学特性计算,得到拟合式后实验通过实验数据验证结果合理性。结果本研究提出的比表面积拟合法在573 K与723 K的温度条件下,计算结果与实验数据一致性较好,但是在623 K与673 K的条件下有较大偏差。结论比表面积拟合法可用于简化计算较大比表面积条件下的Sabatier化学反应的热特性,但是目前该方法并不适应多温度工况,仍需继续完善。

异形催化剂床层中Sabatier反应的微-介尺度模拟

采用离散元方法 (DEM)建立随机堆积球形、柱形催化剂床层,计算流体力学(CFD)方法模拟Sabatier反应床层介尺度和催化剂微尺度的温度和物质浓度分布,并探讨了催化剂形状、壁温和入口条件对反应特征的影响。结果表明:床层中会出现球形热点区,并随反应进行向出口移动,催化剂外层反应物浓度比内层高且呈环状分布。柱形催化剂单颗粒中心CO2转化率较球形高,但棱角和床层壁面会出现低转化率区,床层流体会出现回流、滞留和沟流现象,最终导致CO2转化率为球形>柱形(径高比=1.3)>柱形(径高比=1)。球形催化剂床层中,时间t=200s时,CO2转化率达到峰值26%,若此时将壁温降低50K,时间t=500s时,较降温前CO2转化率增大2%、热点温度降低10K;增加惰性球层、减小入口流速和温度,能提高催化剂内CO2转化率。

Low-temperature dry reforming of methane tuned by chemical speciations of active sites on the SiO_(2) and γ-Al_(2)O_(3) supported Ni and Ni-Ce catalysts

The cognition of active sites in the Ni-based catalysts plays a vital role and remains a huge challenge in improving catalytic performance of low temperature CO_(2) dry reforming of methane(LTDRM).In this work,typical catalysts of SiO_(2) and γ-Al_(2)O_(3) supported Ni and Ni-Ce were designed and prepared.Importantly,the difference in the chemical speciations of active sites on the Ni-based catalysts is revealed by advanced characterizations and further estimates respective catalytic performance for LTDRM.Results show that larger[Ni0-]particles mixed with[Ni-O-Sin])species on the Ni/SiO_(2)(R)make CH_(4) excessive decomposition,leading to poor activity and stability.Once the Ce species is doped,however,superior activity(59.0%CH_(4) and 59.8%CO_(2) conversions),stability and high H_(2)/CO ratio(0.96)at 600℃ can be achieved on the Ni-Ce/SiO_(2)(R),in comparison with other catalysts and even reported studies.The improved performance can be ascribed to the formation of integral([Ni0_(n))]-[CeⅢ-□-CeⅢ])species on the Ni-Ce/SiO_(2)(R)catalyst,containing highly dispersed[Ni]particles and rich oxygen vacancies,which can synergistically establish a new stable balance between gasification of carbon species and CO_(2) dissocia-tion.With respect to Ni-Ce/γ-Al_(2)O_(3)(R),the Ni and Ce precursors are easily captured by extra-framework Al_(n)-OH groups and further form stable isolated([Ni0_(n))]-[Ni-O-Al_(n)])and[CeⅢ-O-Al_(n)]species.In such a case,both of them preferentially accelerate CO_(2) adsorption and dissociation,causing more car-bon deposition due to the disproportionation of superfuous CO product.This deep distinguishment of chemical speciations of active sites can guide us to further develop new efficient Ni-based catalysts for LTDRM in the future.

Interfacial reaction behavior and mechanical properties of 5A06 Al alloy soldered with Sn-1Ti-xGa solders at a low temperature

Active soldering of 5A06 Al alloy was performed at 300 ℃ by using Sn-1Ti and Sn-1Ti-0.3Ga active solders, respectively. Theeffects of soldering time on the microstructure and mechanical properties of the joints were investigated. The results showed that the Sn-1Tisolder broke the oxide film on the surface of the Al substrate and induced intergranular diffusion in the Al substrate. When Ga was added tothe solder, severe dissolution pits appeared in the Al substrate due to the action of Sn-1Ti-0.3Ga solder, and many Al particles were flakedfrom the matrix into the solder seam. Under thermal stress and the Ti adsorption effect, the oxide film cracked. With increasing solderingtime, the shear strength of 5A06 Al alloy joints soldered with Sn-1Ti and Sn-1Ti-0.3Ga active solders increased. When soldered for 90 min,the joint soldered with Sn-1Ti-0.3Ga solder had a higher shear strength of 22.12 MPa when compared to Sn-1Ti solder.

Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

Subject Code:B03With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Ma Ding(马丁)from Peking University,Senior Scientist JoséA.Rodriguez from Brookhaven National Laboratory and Prof.Shi Chuan(石川)from Dalian University of

Atomically dispersed copper species on ceria for the low-temperature water-gas shift reaction

The structure of copper species,dispersed on nanostructured ceria(particles,rods and cubes),was analyzed by scanning transmission electron microscopy(STEM)and X-ray photoelectron spectroscopy(XPS).It was interestingly found that the density of surface oxygen vacancies(or defect sites),induced by the shape of ceria,determined the geometrical structure and the chemical state of copper species.Atomically dispersed species and monolayers containing few to tens of atoms were formed on ceria particles and rods owing to the enriched anchoring sites,but copper clusters/particles co-existed,together with the highly dispersed atoms and monolayers,on cubic ceria.The atomically dispersed copper sites and monolayers interacted strongly with ceria,involving a remarkable charge transfer from copper to ceria at their interfaces.The activity for the low-temperature watergas shift reaction of the Cu/CeO_(2) catalysts was associated with the fraction of the positively-charged copper atoms,demonstrating that the active sites could be tuned by dispersing Cu species on shape-controlled ceria particles.

Investigation of the promotion effect of Mo doped CuO catalysts for the low-temperature performance of NH_(3)-SCR reaction

A novel Mo-doped CuO catalyst is developed and used for low-temperature NH_(3)-SCR reaction.Compared with the undoped CuO sample,the Mo doped CuO catalyst shows an increased SCR performance with above 80%NO_(x) conversion at 175℃.The XRD and Raman results have confirmed the incorporation of Mo metal ions into CuO lattice to form Mo-O-Cu species which may be related to the enhanced SCR activity.The XPS and UV-vis results reveal the creation of electron interaction between Cu and Mo in this Mo-O-Cu system which provides an increased amount of Lewis and Brønsted acid sites,thereby promoting the adsorption capacity of NH_(3) and NO_(x) as verified by NH_(3)-TPD and NO_(x)-TPD characterization.Besides,it also promotes the formation of oxygen vacancies,leading to the increasing of chemisorbed oxygen species,which improves the NO oxidation to NO_(2) activity.Furthermore,in situ DRIFTS technology was also used to study the reaction mechanism of this Mo doped CuO catalyst.The formed NO_(2) could react with NHx(x=3,2)species to enhance the low-temperature NH_(3)-SCR activity via the"fast-SCR"reaction pathway.The nitrate and nitrite ad-species may react with NH_(3) and NH4^(+)ad-species through the L-H pathway.

Low-Temperature Working Feasibility of Zinc–Air Batteries with Noble Metal-Free Electrocatalysts

Expanding the application scenario for rechargeable batteries is the key to the terminal utilization of renewable energy.Enabling zinc–air batteries at low temperatures is drawing increasing attention,yet the low-temperature working feasibility of zinc–air batteries with noble metalfree electrocatalysts remains indistinct.In this contribution,the low-temperature performances of zinc–air batteries with noble metal-free electrocatalysts are comprehensively investigated.Armed with a representative noble metal-free bifunctional oxygen electrocatalyst,the zinc–air batteries demonstrate satisfactory yet relatively depressed performance at low temperatures,compared with that at room temperatures.The reduced electrolyte conductivity is identified as one of the limiting factors for the reduced low-temperature performance.Furthermore,electrolyte engineering via solvation structure regulation is performed on the zinc–air batteries with noblemetal-free electrocatalysts,where an improved low-temperature performance is achieved.This work reveals the compatibility between noble metal-free electrocatalysts and low-temperature feasibility/low-temperature performance enhancement strategies for zinc–air batteries and affords new opportunities to satisfy low-cost and efficient energy storage at harsh working conditions.

Smart tailoring of molecular catalysts:Mounting approach to oxygen reduction reaction

Efficient electrocatalytic rupture of energy-rich molecules(H_(2)and O_(2))is a green approach for gener-ating clean energy for modern societies.In this context,porphyry-type molecular electrocatalysts act intelligently toward oxygen reduction reaction(ORR),a fundamental process in fuel cells,due to their redox-rich chemistry,which involves core metal ions and macrocyclic ligands.The concerned scientific community has tried many times to correlate the ORR intermediates with their formation kinetics and simplify the associated multi H+/e-stages during the ORR process,constructing several volcano plots be-tween catalytic Tafel data,turnover frequencies,and overpotentials for many electrocatalysts.Despite the fact that many review articles on molecular electrocatalysts for ORR have been published,understanding the strategic implications and molecular catalyst intelligence towards homogenous ORR has been poorly explored.This review examined the relationships between volcano plots of current vs.thermodynamic parameters and the Sabatier principle in order to explain the intelligence of molecular electrocatalysts and approaches for their creation,as well as the difficulties and potential prospects of molecular electro-catalysts.These facts distinguish this review from previously published articles and will pique the scien-tific community’s interest in avoiding trial-and-error procedures for catalyst creation while also allowing for more exact evaluations of the molecular catalyst’s performance.

二氧化碳甲烷化还原技术研究

叙述了ＣＯ２还原技术中Ｓａｂａｔｉｅｒ方法的工作原理、实验系统方案、设备和方法等。结果表明：反应器内，在催化剂和一定的温度条件下，ＣＯ２和Ｈ２能生成水和甲烷，为放热反应。实验使用了新研制的高活性钌催化剂，贫组分为ＣＯ２时，一次通过的转化效率为８６．１％～９４．５％，Ｓａｂａｔｉｅｒ反应器内的工作温度范围在３６５～５１５Ｃ内。

火星二氧化碳及水资源利用的研究进展

对于未来火星采样返回、载人火星探测任务而言,火星原位资源利用技术的研究具有必要性。在火星上提取并提前存储火星可用物资,可保障载人火星探测任务甚至火星殖民的需求。基于火星原位资源利用概念,对火星大气可利用的资源进行分析,分别从两大方面(二氧化碳资源和水资源利用)对国内外相关技术的发展情况进行分析,给出宇航员在火星活动和返回舱返回时,获取所需甲烷和氧气的方法。

地外二氧化碳转化利用技术研究现状与展望

为有效解决未来长期载人地外生存面临的物资供给等关键问题,获得更高的氧回收率、能量转化效率和更低的应用成本,亟须发展更高效的地外二氧化碳转化利用技术。文章总结了地外二氧化碳利用的发展现状并分析了近期的研究进展,发现不同技术之间差异大,在航天应用过程中,需充分考虑地外环境限制因素,以选用更合适的技术。空间站上已搭载的Sabatier装置和火星车上的MOXIE装置初步实现了地外二氧化碳还原。以“地外人工光合成”为代表的常温二氧化碳转化技术可为地外环控生保提供新路线。其不仅能够实现地外氧气供给,还可获得甲酸、乙烯和甲烷等有机分子作为燃料或生物转化原料。随着相关基础研究的不断发展,有望实现二氧化碳的高效转化和高附加值有机物、甚至碳糖食物的生产。地外二氧化碳转化利用技术的发展,将实现地外密闭环境下的废弃资源利用与物质循环,降低载人空间站、载人深空飞船的物资供应需求,也将为原位资源利用火星大气中的二氧化碳提供创新思路,以支撑未来可承受、可持续的地外生存任务。

Three-Dimensional Self-assembled Hairball-Like VS4 as High-Capacity Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)are considered to be attractive candidates for large-scale energy storage systems because of their rich earth abundance and consistent performance.However,there are still challenges in developing desirable anode materials that can accommodate rapid and stable insertion/extraction of Na+and can exhibit excellent electrochemical performance.Herein,the self-assembled hairball-like VS4 as anodes of SIBs exhibits high discharge capacity(660 and 589 mAh g−1 at 1 and 3 A g−1,respectively)and excellent rate property(about 100%retention at 10 and 20 A g−1 after 1000 cycles)at room temperature.Moreover,the VS4 can also exhibit 591 mAh g−1 at 1 A g−1 after 600 cycles at 0°C.An unlike traditional mechanism of VS4 for Na+storage was proposed according to the dates of ex situ characterization,cyclic voltammetry,and electrochemical kinetic analysis.The capacities of the final stabilization stage are provided by the reactions of reversible transformation between Na2S and S,which were considered the reaction mechanisms of Na–S batteries.This work can provide a basis for the synthesis and application of sulfur-rich compounds in fields of batteries,semiconductor devices,and catalysts.

Effect of Magnetic Field on Synthesis of Nano-FeOOH by Low-Temperature Neutralization Method

Using XRD,TEM and VSM methods,the phase,morphology and magnetic property of iron hydroxide oxide(FeOOH) which has been prepared by low-temperature neutralization reaction under different magnetic fields were analyzed.It can be found that the magnetic field had a great influence on the product.Acicular goethite(α-FeOOH) was synthetized without magnetic field.When the magnetic flux density was increased to 0.1T,γ-FeOOH was obtained.If the magnetic field intensity was raised to 0.5T,the product was all composed of δ-FeOOH.Moreover,the crystallization of FeOOH was greatly influenced by magnetic field as well.Thermodynamic calculation results show that the magnetic free energy of chemical reaction reached to more than hundreds KJ/mol when the magnetic field is applied.It meaned that the application of magnetic field was conducived to producing the products with higher susceptibility.Even under the low magnetic field,due to the stability of the reaction products was broken by the magnetic field,the magnetic free energy was also effective.