SnO_2-based solid solutions for CH_4 deep oxidation: Quantifying the lattice capacity of SnO_2 using an X-ray diffraction extrapolation method

A series of SnO2‐based catalysts modified by Mn, Zr, Ti and Pb oxides with a Sn/M （M=Mn, Zr, Ti and Pb） molar ratio of 9/1 were prepared by a co‐precipitation method and used for CH4 and CO oxidation. The Mn3＋, Zr4＋, Ti4＋and Pb4＋cations are incorporated into the lattice of tetragonal rutile SnO2 to form a solid solution structure. As a consequence, the surface area and thermal stability of the catalysts are improved. Moreover, the oxygen species of the modified catalysts become easier to be reduced. Therefore, the oxidation activity over the catalysts was improved, except for the one modified by Pb oxide. Manganese oxide demonstrates the best promotional effects for SnO2. Using an X‐ray diffraction extrapolation method, the lattice capacity of SnO2 for Mn2O3 was 0.135 g Mn2O3/g SnO2, which indicates that to form stable solid solution, only 21%Sn4＋cations in the lattice can be maximally replaced by Mn3＋. If the amount of Mn3＋cations is over the capacity, Mn2O3 will be formed, which is not favorable for the activity of the catalysts. The Sn rich samples with only Sn‐Mn solid solution phase show higher activity than the ones with excess Mn2O3 species.

Highly efficient and selective photocatalytic dehydrogenation of benzyl alcohol for simultaneous hydrogen and benzaldehyde production over Ni-decorated Zn_(0.5)Cd_(0.5)S solid solution

Photocatalytic conversion of solar energy into hydrogen and high value-added fine chemicals has attracted increasing attention. Herein, we demonstrate an efficient photocatalytic system for simultaneous hydrogen evolution and benzaldehyde production by dehydrogenation of benzyl alcohol over Nidecorated Zn_(0.5)Cd_(0.5)S solid solution under visible light. The photocatalytic system shows an excellent hydrogen production rate of 666.3 μmol h^(-1) with high stability. The optimal apparent quantum yield of52.5% is obtained at 420 nm. This noble-metal-free photocatalytic system displays much higher activity than pure Zn_(0.5)Cd_(0.5)S and Pt-loaded Zn_(0.5)Cd_(0.5)S solid solution. Further studies reveal that the metallic Ni nanocrystals play an important role in accelerating the separation of photogenerated charge carriers and the subsequent cleavage of α-C–H bond during dehydrogenation of benzyl alcohol.

Synthesis and Electrochemical Property of Calcium Doped LiNi0.8Co0.2O2 Solid Solution

A divalent ion doped LiNi0.8Co0.2O2 solid solution, LiNi0.79Co0.20Ca0.01O2, was synthesized in air at 720℃. The structure and electrochemical property as cathode material of lithium ion batteries were measured by XRD and charge-discharge system. The solid solution showed high capacity and good cycle-ability. The second discharged capacity reached 190 mAh穏-1 at the current density of 100 mA穏-1.

Catalytic reduction of SO_2 by CO over CeO_2-TiO_2 mixed oxides

The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n（Ce）：n（Ti） is 5：5 or greater, and the most suitable n（Ce）：n（Ti） isdetermined as 7：3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 （n（Ce）：n（Ti）=7：3） without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2＋CO reaction show that CeO2 is the active component that offers the redox couple Ce4＋/Ce3＋ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.

In situ regulating intimately connected heterostructure by decomposition of solid solution oxides toward high-efficient water oxidation

Heterogeneous interfaces produced by interdomain interactions on a nanoscale performs a crucial role in boosting the properties of an electrocatalyst toward oxygen evolution reaction(OER)process.Herein,a series of dual-phase electrodes with intimately connected heterointerfaces are prepared by in situ decomposing solid solution oxide of Ni_(x)Co_(y)Fe_(100-x-y)O,which grew on Ni foam massively via an ultrafast combustion approach.Particularly,with high-reaction kinetics caused by the reduction treatment at 450℃,the less electronegative Fe and Co are more oxyphilic than Ni,which facilitated their co-exsolution and formation of CoFe_2O_4/NiO oxide with enriched oxygen vacancies.Benefiting from the nanoporous framework,heterojunction structure,and oxygen defects,the self-supporting electrodes present rapid charge/mass transmission and provide abundant active sites for OER.The optimized sample(R-SNCF4.5)shows low overpotentials of 226 and 324 mV at 10 and100 mA·cm^(-2),a small Tafel slope(46.7 mV·dec^(-1)),and excellent stability.The assembled R-SNCF4.5//Pt/C/NF electrolyzer demonstrates continuous electrolysis over 50 h at a current density of 10 mA·cm^(-2),under 1.51 V.Density functional theory(DFT)calculations verify that the strong electronic modulation plays a critical part in the CoFe_2O_4/NiO hybrid by lowering the energy barriers for the ratedetermining steps,and Fe sites are the most active OER sites.

Catalytic performance for methane combustion of supported Mn-Ce mixed oxides

A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption （BET）, X-ray diffraction （XRD）, laser Raman spectrum （LRS）, and temperature programmed reduction （TPR） techniques. The XRD and LRS results confirmed the high dispersion of active components or formation of solid solution between manganese and cerium oxides in the bulk and on the surface of mixed oxide catalysts. The reducibility was remarkably promoted by the stronger synergistic interaction between the two oxides from H2-TPR measurements. As expected, all the experimental mixed oxide catalysts showed excellent activity for methane combustion at low temperature. Especially, for the catalyst with Mn-Ce ratio 3：7, methane conversion reached 92% at a temperature as low as 470 ℃.

A rationale for the development of thermally stable nanostructured CeO_2-ZrO_2-containing mixed oxides

CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.

Influence of La precursors on structure and properties of CeO_2-ZrO_2-Al_2O_3 composite oxides

Three La-doped CeO2-ZrO2-Al2O3(CZA)composite oxide samples,namely,CZA-I,CZA-II and CZA-III,were prepared following a co-precipitation method in the presence of La2O3,La(NO3)3-6H2O and H[La(EDTA)]-16H2O precursors,respectively.When the precursor samples are sintered at 1000°C,the as-prepared composite oxides mainly exhibit the CeO2-ZrO2 cubic fluorite phase,while theγ-Al2O3 andδ-Al2O3 phases appear when the precursor samples are subjected to sintering at 1100 and 1200°C.CZA-III exhibits improved redox properties after high-temperature treatment compared with CZA-I and CZA-II.CZA-III presents the largest surface area of 97.46 m2/g among the three CZAs when the CZA-III precursor sample is sintered at 1000°C.Furthermore,the corresponding oxygen storage capacity(OSC)is the largest with value of 400.27μmol/g when CZA-III precursor sample is sintered at 1000°C.Additionally,CZA-III exhibits the best thermal stability and the highest reduction temperature.However,by increasing the sintering temperature to 1200°C,there is a dramatic decline in the properties of surface area and OSC.And a decrease for CZA-III in surface area by 58.94%and a decrease of the OSC value by 74.56%are observed.

Characteristics of Magnesium-iron-aluminium Composite Oxides and Their Influence on Properties of Magnesia-based Bricks

The composition,structure and micro-morphology of magnesium- iron- aluminum composite oxides were investigated using various methods such as XRF,SEM,EDS,XRD and KMn O4-titration. Compared to hercynite,the composite oxides have completely different phases including solid solution（ Mg O）0. 77（ Fe O）0. 23,composite spinel Mg Fe0. 2Al1. 8O4 and a small amount of Mg Fe2O4. The composite oxides exhibit excellent corrosion resistance to cement clinker and potassium salts.The products produced by magnesite and the composite oxides show better performance than magnesia- hercynite bricks,especially the corrosion resistance and thermal shock resistance.

Ce-Zr-Mn-O固溶体作为甲烷燃烧过渡金属催化剂载体的研究

用溶胶凝胶法制备了不同锰含量的 Ce Zr Mn O固溶体,样品在老化前后均用 XRD、TPR表征,并测定其储氧性能。结果表明锰含量对该储氧材料(OSM)的储氧性能有很大的影响:样品的储氧量(OSC)老化前随着 Mn含量的增加而增加;老化后则先增加而后又降低,以 Mn含量 20%为最佳。以不同比例的OSM(含 20%锰)YSZ Al2O3 为载体制备了一系列Fe、Co、Mn三组分氧化物的整体式催化剂,考察了它们的甲烷催化燃烧活性。结果表明老化前后,Fe Co Mn/OSM+YSZ Al2O3 (其中 OSM和 YSZ Al2O3质量比为1∶1)活性明显高于Fe Co Mn/YSZ Al2O3,且具有可与贵金属催化剂相比美的特性———较低的起燃温度、很窄的完全反应温度区间,同时兼有较好的热稳定性,有望成为实用的甲烷燃烧催化剂。

甲烷完全氧化反应的Cu/Ce-Zr-O固溶体电催化剂

采用X射线衍射(XRD)、X光电子能谱(XPS)和程序升温还原(TPR)等手段,对以甲烷为燃料的固体氧化燃料电池阳极催化剂———Cu掺杂Ce-Zr-O固溶体进行了研究.结果表明:溶胶-凝胶法制备的催化剂中ZrO2四方晶相含量最高,其次是共沉淀法,含量最低的是浸渍法;溶胶-凝胶法制备的催化剂中嵌入Ce-Zr-O固溶体晶格并为后者所高度分散和稳定的Cu相对较多,而浸渍法制备的催化剂表面以晶相CuO形式存在的Cu相对较多.当Cu的掺杂量增大时,催化剂表面过氧物种O22-(或氧自由基O-)的浓度增加;CeO2的添加可以明显提高催化剂表面O22-或O-等过氧物种的浓度.研究结果与Cu掺杂Ce-Zr-O固溶体在甲烷的完全氧化反应中表现出的催化活性有较好的对应关系.

Selective oxidation of methane to syngas using Pr_(0.7)Zr_(0.3)O_(2-δ): Stability of oxygen carrier

Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical properties of Pr0.7Zr0.3O2-δ during the redox process was studied by means of X-ray diffraction(XRD), H2 temperature-programmed reduction(H2-TPR), O2temperature-programmed desorption(O2-TPD), Brunauer-Emmett-Teller(BET) surface area measurement and X-ray photoelectron spectroscopy(XPS) technologies. The results indicated that Pr0.7Zr0.3O2-δ solid solution showed the high activity for the methane conversion to syngas with a high CO selectivity in the range of 83.5%-88.1%. Though Pr-Zr solid solution possessed high thermal stability, lattice oxygen was obviously reduced for the recycled sample due to decreased surface oxygen which promoted oxygen vacancies. The increased oxygen vacancies seemed to enhance the oxygen transfer ability in the redox process and provided sufficient oxygen for the methane selective oxidation, resulting in a satisfactory activity. The problem of hot pot was avoided by comparing fresh, aged and recycle sample in the reaction.

Ce-Zr-O2上CuO分散性对CO氧化活性的影响

采用柠檬酸法制备了Ce-Zr-O2固溶体,并负载了过渡金属和贵金属Pt,其中,以Cu作为活性组分,在CO氧化反应中表现出最高的活性,CO完全转化的温度约为120℃,明显高于负载1%Pt(质量分数)催化剂的活性.掺杂少量Zr到Ce O2(Ce0.8Zr0.2O2)中对Cu基催化剂有非常好的促进作用.分别采用等体积浸渍法(IW)、沉淀沉积法(DP)、水热法(HT)以及柠檬酸法(CA)制备了Cu负载质量分数为20%的Cu/Ce0.8Zr0.2O2催化剂.结果表明,由沉淀沉积法制备的Cu/Ce0.8Zr0.2O2催化剂的活性最高,在100℃时,CO可完全转化.TEM结果表明,Cu O物种很好地分散在Ce0.8Zr0.2O2上.吸附实验数据表明,Cu基催化剂上CO与O2之间较弱的竞争吸附是其活性高于Pt催化剂的主要原因.Cu基催化剂上的氧空位对促进O2的吸附具有重要作用,也是影响CO低温氧化的重要因素之一.

Cu-Ce-Zr-Ba-O复合氧化物催化剂的制备与三效催化性能

采用共沉淀法和等体积浸渍法,分别研制Cu-Ce-Zr-Ba-O复合氧化物催化剂.催化活性的测定结果表明:当Ce与Zr的摩尔比为0.2︰0.8,Ba含量为4%,Cu负载量为5%时,采用等体积浸渍法制备的Cu-Ce-Zr-Ba-O复合氧化物具有更好的三效催化活性,能使C3H6、CO、NO的转化率分别高达99.4%、97.5%、99.9%.XRD和DTA的测试分析结果也表明:Ba的加入会形成铈锆钡(Ce-Zr-Ba)固溶体,有助于提高催化剂的活性和热稳定性,因此所制得的复合氧化物具有良好的三效催化性能.

Chromium-ruthenium oxide solid solution electrocatalyst for highly efficient oxygen evolution reaction in acidic media

With the support of the National Natural Science Foundation of China and the aided program for Science and Technology Innovative Research Team of Ningbo Municipality,the research team led by Prof.ChenLiang(陈亮)at Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,reported a chromium-ruthenium oxide solid solution electrocatalyst for the highly efficient oxygen evolution reaction(OER)in acidic media.

Catalytic Hydrogenation of Acetic Acid to Acetaldehyde: Synergistic Effect of Bifunctional Co/Ce-Fe Oxide Solid Solution Catalysts

The large-scale industrial production of acetic acid (HAc) from carbonylation of methanol has enabled intense research interest from direct hydrogenation of HAc to acetaldehyde (AA).Herein,a series of cerium-iron oxide solid solution supported metallic cobalt catalysts were prepared by modified sol-gel method and were applied in gas-phase hydrogenation of HAc to AA.A synergistic effect between the hydrogenation metal cobalt and Ce-Fe oxide solid solution is revealed.Specifically,oxygen vacancies provide the active sites for adsorption of HAc,while highly uniformly dispersed metallic Co adsorbs H2 and activates the reduction of HAc into AA.Moreover,the metallic Co can also assist the cyclical conversion between Fe3+/Fe2+ and Ce3+/Ce4+ on the surface of Ce1.xFexO2-δ supports.The unique effect substantially enhances the ability of the support material to rapidly capture oxygen atoms from HAc.It is found that the catalyst of 5% Co/Ce0.8Fe0.2O2-δ with the highest concentration of oxygen vacancy presents the best catalytic performance (i.e.acetaldehyde yield reaches 49.9%) under the optimal reaction conditions (i.e.623 K and H2 flow rate =10 mL/min).This work indicates that the Co/Ce-Fe oxide solid solution catalyst can be potentially used for the selective hydrogenation from HAc to AA.The synergy between the metallic Co and Ce1-xFexO2-δ revealed can be extended to the design of other composite catalysts.

Effect of Zr-doping on Pd/CexZr1-xO2 catalysts for oxidative carbonylation of phenol

Ce–Zr solid solution(CexZr1-xO2,CZO)was prepared by the citric acid sol–gel method.The CZO was then used as a support for Pd/CZO catalysts for the oxidative carbonylation of phenol to diphenyl carbonate.The Pd/CZO catalyst showed enhanced activity and diphenyl carbonate selectivity compared with the Pd/CeO2 catalyst.The catalytic performance of Pd/CZO was influenced by the calcination temperature of the CZO support.X-ray diffraction,scanning electron microscopy,N2 adsorption–desorption measurements,X-ray photoelectron spectroscopy and H2 temperature-programmed reduction measurements were used to investigate the effects of Zr doping and calcination temperature.The catalytic performance of Pd/CZO and Pd/CeO2 for the oxidative carbonylation of phenol was affected by several factors,including the specific surface area,Ce^3+and/or oxygen vacancy content,oxygen species type and Pd(II)content of the catalyst.All these properties were influenced by Zr doping and the calcination temperature of the CZO support.

过渡金属改性Ce-Zr固溶体催化氧化丙烯和CO

丙烯和CO是大气中主要的有害气体,需有效去除。选取Cu,Co,Ni,Fe为活性组分,采用共沉淀法制备过渡金属M(M=Cu,Co,Ni,Fe)与Ce+Zr+M原子比为1∶40的复合氧化物催化剂(M-CZO)催化燃烧两种有害气体,并采用XRD,BET,TPR对催化剂进行了表征。结果表明,过渡金属改性Ce-Zr固溶体对两种气体催化活性相对CZO大大提高。其中催化氧化CO时,活性顺序为Cu>Co>Ni>Fe,Cu-CZO活性最高,T50和T90分别为95℃和185℃。H2-TPR结果表明,表面氧越活泼,催化氧化CO的活性越高。C3H6催化氧化活性顺序为Co>Cu>Fe>Ni,随着温度升高,CO相对生成量增加,Cu-CZO催化氧化CO活性远高于其他三种催化剂,使C3H6→CO→CO2连续反应快速进行,从而使C3H6总转化率提高,导致Co-CZO的T90比Cu-CZO略高。整体看来,Cu-CZO催化燃烧C3H6效果最好,T50和T90分别为345℃和376℃,CO的浓度低于0.05 mg/L,二次污染最小。

In-situ assembly of 2D/3D porous nickel cobalt sulfide solid solution as superior pre-catalysts to boost multi-functional electrocatalytic oxidation

In this work,we fabricated an efficient pre-catalyst based on(Ni,Co)S2solid solution with hierarchical architecture and high porosity to boost urea oxidation reaction and electrocatalytic oxidation of organic small molecules.The interaction between Ni and Co can optimize the electronic structure,resulting in the improved conductivity and accelerated charge transfer rate.The 2D/3D architecture can enrich more active species and endow the mass and electron transport to facilitate the surface oxidation and the following catalytic process.Post-structure and catalytic characterizations confirm the surface oxidation of(Ni,Co)S_(2)during the stability test,and the in-situ formed Co(Ni)based(oxy)hydroxides exhibit superior catalytic activity and facilitated charge transfer ability.As a result,the optimal(Ni,Co)S_(2)solid solution pre-catalyst displays facilitated catalytic behavior and good stability for multifunctional electrocatalytic oxidation,in which a high conversion of benzyl alcohol(97.50%),a good selectivity to benzoic acid(93.78%)and a satisfied faraday efficiency(91.86%)can be achieved.

Estimation of component activities in some oxide solid solutions by the molecular interaction vacancy model

The molecular interaction vacancy model （MIVM） is used to estimate simultaneously activities of all components in a range of entire composition of six binary oxide solid solutions and the MnO-FeO-CaO ternary solid solution by their binary infinite dilute activity coefficients. The average errors are the 0.03%-5.0% for the binaries and the 4.11%-25.2% for the ternary which is less than that （4.84%-41.2%） of the sub-regular solution model （SRSM）. This shows that MIVM is more effective and reliable than SRSM for the ternary and does not depend on a polynomial approximation with some ternary adjustable parameters.