Understanding the Role of Gold Nanoparticles in Enhancing the Catalytic Activity of Manganese Oxides in Water Oxidation Reactions

The Earth‐abundant and inexpensive manganese oxides (MnO_x) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnO_x catalysts are still much lower than that of nanostructured IrO₂ and RuO₂ catalysts. Herein, we demonstrate that doping MnO_x polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnO_x/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn³⁺ species, a small amount of AuNPs (<5 %) in α‐MnO₂/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α‐MnO₂.     

MnOx-SnO2 Catalysts Synthesized by a Redox Coprecipitation Method for Selective Catalytic Reduction of NO by NH3

MnO_x-SnO₂ composite oxides prepared by a redox coprecipitation route were tested in selective catalytic reduction of NO by NH₃ at low temperatures. The results showed that the MnO_x-SnO₂ catalyst with a Mn/(Mn+Sn) molar ratio of 75% exhibited the best performance, on which NO conversion of 100% could be achieved at temperatures of 120–200 °C. The characterization results of N₂ adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy indicated that the higher surface area, the formation of solid solution between manganese and tin oxides, and the high oxidation state manganese species were responsible for the high catalytic activity of the MnO_x-SnO₂ catalyst.     

Natural hydroxyapatite‐supported MnO2: a green heterogeneous catalyst for selective aerobic oxidation of alkylarenes and alcohols

Natural hydroxyapatite‐supported MnO₂ (MnO₂@NHAp) was easily prepared in situ from reduction of potassium permanganate with natural hydroxyapatite derived from cow bones in water at room temperature, and its structure was characterized using flame atomic absorption spectroscopy, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive spectroscopy. The catalytic activity of the synthesized catalyst was investigated for the aerobic oxidation of alkylarenes and alcohols. MnO₂@NHAp shows excellent catalytic performance for the oxidation of alkylarenes and alcohols to their corresponding carbonyl compounds without using any other oxidizing agent. This catalyst can be readily recycled and reused for several runs without any significant loss of efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

Novel Catalytic Dielectric Barrier Discharge Reactor for Gas-Phase Abatement of Isopropanol

Catalytic gas-phase abatement of air containing 250 ppm of isopropanol (IPA) was carried out with a novel dielectric barrier discharge (DBD) reactor with the inner catalytic electrode made of sintered metal fibers (SMF). The optimization of the reactor performance was carried out by varying the voltage from 12.5 to 22.5 kV and the frequency in the range 200–275 Hz. The performance was significantly improved by modifying SMF with Mn and Co oxide. Under the experimental conditions used, the MnO _x /SMF showed a higher activity towards total oxidation of IPA as compared to CoO _x /SMF and SMF electrodes. The complete destruction of 250 ppm of IPA was attained with a specific input energy of ∼235 J/L using the MnO _x /SMF catalytic electrode, whereas, the total oxidation was achieved at 760 J/L. The better performance of the MnO _x /SMF compared to other catalytic electrodes suggests the formation of short-lived active species on its surface by the in-situ decomposition of ozone.     

Influence of the mobility of oxygen on the reactivity of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> perovskites in methane oxidation

Radically different dependences of the activity of La_{1 − x} Sr _x MnO₃ (x = 0−0.5) perovskites in methane oxidation on the degree of substitution of strontium for lanthanum are observed for low and high temperatures. Unsubstituted LaMnO₃ exhibits the highest activity in the temperature range from 300 to 500°C, while the sample with the maximum degree of substitution (La_0.5Sr_0.5MnO₃) shows the highest activity at higher temperatures of 700–900°C. In the low temperature region, the activity of La_{1t - x} Sr _x MnO₃ is determined by the amount of weakly bound (overstoichiometric) oxygen, which is formed in cation-deficient lattices and is characterized by a thermal desorption peak with T _max = 705°C. At higher temperatures (800–900°C), the strongly bound oxygen of the catalyst lattice is involved in the formation of the reaction products under both unsteady- and steady-state conditions. As a consequence, the catalytic activity in methane oxidation correlates with the apparent rate constant of oxygen diffusion in the oxide bulk.     

Development of the bifunctional catalyst Mn-Fe-Beta for selective catalytic reduction of nitrogen oxides

The catalytic properties of the Mn-Fe-Beta system with Mn contents in the range 0.1–16 wt.% were studied in the selective catalytic reduction (SCR) of NO _x with ammonia. The catalyst structure was investigated using IR spectra of adsorbed NO, temperature-programmed reduction with hydrogen (H₂-TPR), X-ray diffraction analysis, and ESR. The use of manganese as a promoter substantially increases the activity of iron-containing catalysts in the SCR of NO _x with ammonia. At low contents (<2 wt.%), Mn exists in the cation form and the catalytic activity of the Mn-Fe-Beta system does not increase. At a higher content of Mn, clusters MnO _x begin to form, which are highly active in the oxidation of NO to NO₂ and the low-temperature catalytic activity of the Mn-Fe-Beta system increases. The observed increase in the low-temperature catalytic activity in the process of SCR of NO _x with ammonia is related to a change in the reaction route. The MnO _x clusters favor the oxidation of NO and the iron cations facilitate the reaction of “fast” SCR.     

MnO2-0.39IrOx复合氧化物用于酸性介质中水氧化反应的性能

通过Adams方法成功制备MnO₂-0.39IrO_x(0.39为Ir/Mn的原子比)催化剂并将其用于酸性介质中高效析氧反应(OER)。电化学测试发现,MnO₂-0.39IrO_x仅需253 mV的过电势即可驱动10 mA·cm^-2的水氧化电流密度,并可稳定运行200 h。在1.50 V(vs RHE)电势下,MnO₂-0.39IrO_x的贵金属Ir的质量活性为61.3 mA·mg^-1,是IrO₂的35.8倍,说明MnO₂掺杂大大提升了贵金属利用率。结构分析发现MnO₂-0.39IrO_x独特的片状结构大幅度提高了催化剂的电化学活性表面积,并且Ir位点与Mn位点之间存在一定的电子相互作用。催化过程分析表明,MnO₂-0.39IrO_x表面出现一定的重构现象,并且Mn组分对Ir位点的化学环境实现了持续优化,从而实现了催化剂的高效酸性OER性能。     

La1-xCaxMnO3纳米颗粒的制备及氧还原催化性能

本文采用溶胶凝胶法制备了一系列不同Ca含量的钙钛矿型氧化物La_1-xCa_xMnO₃(x=0~0.4)纳米颗粒, X射线粉末衍射及精修、扫描电镜表征显示其相纯度和结晶度高, 颗粒平均粒径约40 nm。在0.1 mol·L^-1 KOH水溶液中进行的氧还原电催化性能测试显示, La_0.7Ca_0.3MnO₃样品催化活性最高, 表观电子转移数接近4, 还原电流密度与Pt/C催化剂相当, 而催化稳定性优于Pt/C。进一步研究了La_1-xCa_xMnO₃样品中Mn价态、晶胞参数的改变对氧还原催化活性的影响, 结果表明当x=0.3时, 催化剂中Mn处于混合价态, Mn-O键长适中, 最有利于电催化反应。     

La1-xCaxMnO3纳米颗粒的制备及氧还原催化性能

本文采用溶胶凝胶法制备了一系列不同Ca含量的钙钛矿型氧化物La1-xCaxMnO3(x=0~0.4)纳米颗粒,X射线粉末衍射及精修、扫描电镜表征显示其相纯度和结晶度高,颗粒平均粒径约40 nm。在0.1 mol.L-1KOH水溶液中进行的氧还原电催化性能测试显示,La0.7Ca0.3MnO3样品催化活性最高,表观电子转移数接近4,还原电流密度与Pt/C催化剂相当,而催化稳定性优于Pt/C。进一步研究了La1-xCaxMnO3样品中Mn价态、晶胞参数的改变对氧还原催化活性的影响,结果表明当x=0.3时,催化剂中Mn处于混合价态,Mn-O键长适中,最有利于电催化反应。     

Porous chitosan–MnO2 nanohybrid: a green and biodegradable heterogeneous catalyst for aerobic oxidation of alkylarenes and alcohols

A porous chitosan–manganese dioxide (PC–MnO₂) nanohybrid was synthesized using an in situ reduction method, in which potassium permanganate solution and nanoporous chitosan acted as precursor and reducing agent. The chemical and structural properties of PC–MnO₂ were characterized using scanning and transmission electron microscopies, X‐ray diffraction, thermogravimetric analysis and Fourier transform infrared spectroscopy. Highly dispersed MnO₂ nanoparticles in a matrix of porous chitosan showed high catalytic activity for selective aerobic oxidation of alkylarenes and alcohols without using any bases or expensive oxidants. Short reaction time, ease of product separation by filtration and recyclability of the catalyst make it environmentally and economically favoured for the synthesis of versatile aldehydes and ketones. Copyright © 2015 John Wiley & Sons, Ltd.     

MnOx/Al-SBA-15的结构性质及低温NH3选择性催化还原NOx

采用后合成法制备MnO_x/Al-SBA-15催化剂, 考察了催化剂的低温NH₃选择性催化还原(SCR)NO_x的性能. 利用傅里叶透射红外变换(FTIR)光谱、N₂吸附-脱附、X射线衍射(XRD)、扫描电镜(SEM)、拉曼光谱(Raman)、X射线光电子能谱(XPS)及NH₃程序升温脱附(NH₃-TPD)的表征手段, 对催化剂的结构性质和SCR性能进行了系统分析. 结果表明, 适量Al的掺杂能提高MnO_x/SBA-15催化剂的SCR活性, 当硅铝摩尔比为50时, 催化剂活性最佳. 表征结果显示, Al掺杂后, 催化剂仍保持良好的骨架结构, 较大比表面、孔容和孔径, 并且Mn在催化剂表面富集, 由低价态转化为高价态, MnO₂为催化剂的主要活性相. 此外, Al的掺杂使MnO_x在催化剂表面高度分散, 表面酸性增强, 从而提高了催化剂的SCR活性.     

Mn负载量对nMnO_x/TiO_2催化剂NH_3-SCR催化性能的影响

MnO_x/TiO_2催化剂由于具有优异的低温脱硝性能,已成为SCR催化剂的研究热点之一.我们通过浸渍法制备了一系列不同Mn负载量的nMnO_x/TiO_2(n=2.5%, 5%, 10%, 15%)(质量分数)催化剂,考察Mn负载量对催化剂脱硝性能的影响.利用N_2物理吸附, X-Ray Diffraction (XRD), Scanning Electron Microscope(SEM),Temperature Programmed Reduction with H_2(H_2-TPR),Temperature Programmed Desorption with NH_3(NH_3-TPD)和X-Ray Photoelectron Spectroscopy (XPS)对其结构进行表征.结果表明,催化剂的脱硝性能随着Mn负载量(2.5%～15%)(质量分数)的变化呈现"火山型"曲线,当Mn负载量为10%(质量分数)时,催化剂的脱硝性能最佳. H_2-TPR和XPS结果表明nMnO_x/TiO_2催化剂上表面氧比例和表面Mn~(4+)浓度均随着Mn负载量的增大,先增大后减小,具体顺序为10MnO_x/TiO_(2 ) 15MnO_x/TiO_(2 )5MnO_x/TiO_(2 ) 2.5MnO_x/TiO_2,与脱硝性能顺序完全一致.进一步关联表面氧的比例与T_(50)发现,催化剂的表面氧的比例与T_(50)呈线性关系,即表面氧比例越高, T_(50)越小,脱硝活性越高. NH_3-TPD结果表明,弱酸酸量的增加有助于低温脱硝活性的提高.这些结果揭示了Mn负载量影响脱硝性能的作用规律,为今后开发高效的锰基低温脱硝催化剂提供了技术支撑.     

Synthesis of homogeneous La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> solid solutions by the Pechini method and their activity in methane oxidation

Homogeneous La_{1 − x} Ca _x MnO₃ solid solutions have been synthesized by the Pechini method (using polymer-solid compositions). Their microstructure, stability at high temperatures, and catalytic activity in methane oxidation are reported. A continuous series of solid solutions stable in air up to 1100°C forms in the system, and the particle surface is enriched with calcium. A distinctive microstructural feature of the particles is their microporosity. The catalytic activity of all calcium-containing samples (except for x = 0.7) below 700°C is lower than that of lanthanum manganite and decreases under the action of the reaction medium, which can be due to the decrease in the amount of weakly bound oxygen on the surface because of the enrichment of the surface with calcium and the formation of strongly bound surface carbonates. The higher activity and stability of the La_0.3Ca_0.7MnO₃ sample (calcined at 1100°C) above 500°C can be due to the formation of nanosized areas with an Mn₃O₄ structures on the perovskite particle surface in the reaction medium.     

浸渍法制备的Pd-MnO_x/γ-Al_2O_3催化剂及不同载体对地表O_3降解的影响(英文)

在γ-Al2O3载体上用等体积浸渍法浸渍Pd、MnOx活性组分,然后涂覆于堇青石基体上制备Pd-MnOx/γ-Al2O3整体式催化剂.分别用X射线衍射(XRD)、H2-程序升温还原(H2-TPR)、低温N2吸附-脱附及X射线光电子能谱(XPS)对制备的催化剂进行表征.研究了Pd、MnOx浸渍顺序对催化剂活性、氧化还原性能及织构性质的影响.实验结果表明,Pd、MnOx共浸渍较分别浸渍制备的催化剂活性好,Pd和MnOx之间存在一定的协同作用.考察了不同载体如La-Al2O3、SiO2、γ-Al2O3和Zr-Al2O3对催化剂活性、氧化还原性能、织构性质及表面电子性能的影响.研究表明,以La-Al2O3或SiO2为载体的催化剂活性最好,即,14°C时O3转化率为82%,完全转化温度为36°C.γ-Al2O3载体次之,Zr-Al2O3载体较差.不同载体制备的催化剂中MnOx的氧化还原性能顺序为:PdMnOx/SiO2Pd-MnOx/La-Al2O3Pd-MnOx/γ-Al2O3Pd-MnOx/Zr-Al2O3.     

An effect of heat processing on catalytic activity of a system MnO x ,SiO2/TiO2/Ti

An effect of annealing in air at temperatures 250, 350, 500, and 700°C on composition, surface structure, and catalytic activity in CO oxidation of a system MnO _x ,SiO₂/TiO₂/Ti formed by combining methods of plasma electrolytic oxidation and impregnation was examined.     

Influence of hydrothermal synthesis temperature on the redox and oxygen mobility properties of manganese oxides in the catalytic oxidation of toluene

A series of MnO_x samples synthesized by hydrothermal methods at different temperatures were investigated as catalysts for the oxidation of toluene. The optimum oxidation performance was achieved with the catalyst prepared at 120 °C (Mn-120), for which complete conversion of toluene was attained at 250 °C. The Mn-120 sample possessed the highest concentration of Mn³⁺ and the highest initial H₂ consumption rate, which are indicative of abundant crystal defects and superior reducibility. In addition, Mn-120 exhibited excellent oxidation ability due to the abundance of lattice oxygen species and excellent oxygen mobility. Therefore, the superior catalytic performance of Mn-120 could be attributed mainly to its redox performance and abundant crystal defects, both of which are determined by the temperature of the hydrothermal synthesis of MnO_x.

     

酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用

利用溶胶-凝胶法,采用三种酸性金属氧化物（氧化铌、氧化钨和氧化钼）对锰铈复合氧化物催化剂进行了改性. 测试了催化剂的氮氧化物选择性催化还原（SCR）活性,以筛选对应不同温度窗口的合适酸性氧化物改性剂. 同时评价了催化剂的NO氧化和NH₃氧化活性. 利用X射线衍射、BET比表面积测试、H₂程序升温还原、NH₃/NO_x程序升温脱附和NH₃/NO_x吸附红外光谱等手段对催化剂进行了表征. MnO_x-CeO₂催化剂表现出良好的低温（100-150 ℃）活性. 酸性金属氧化物的添加削弱了催化剂的氧化还原特性,从而抑制了NH₃的活化和NO₂辅助的快速SCR反应. 与此同时,相对高温（250-350 ℃）区NH₃的氧化也受到了抑制,B酸和L酸上的NH₃吸附得以增强. 因此,催化剂的SCR脱硝温度窗口向高温移动,改性效果Nb₂O₅ < WO₃ < MoO₃.     

Catalytic Performance of MnOx Nanorods in Aerobic Oxidation of Benzyl Alcohol

Various manganese oxide nanorods with similar one-dimensional morphology were prepared by calcination of MnOOH nanorods under different gas atmosphere and at different temper-atures, which were synthesized by a hydrothermal route. The morphology and structure of MnO_x catalysts were characterized by a series of techniques including X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and tempera-ture programmed reduction (TPR). The catalytic activities of the prepared MnO_x nanorods were tested in the liquid phase aerobic oxidation of benzyl alcohol, which follow a sequence as MnO₂>Mn₂O₃≈Mn₃O₄>MnOOH with benzaldehyde being the main product. On the basis of H₂-TPR results, the superior activity of MnO₂ is ascribed to its lower reduction temperature and therefore high oxygen mobility and excellent redox ability. Moreover, a good recycling ability was observed over MnO₂ catalysts by simply thermal treatment in air.     

Cyclic voltammetric study on the catalysis of electrodeposited manganese oxide on the electrochemical oxygen reduction reaction (ORR) in room temperature ionic liquids (RTILs) of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF<Subscript>4</Subscript>) on glassy carbon clectrode

For the first time, the electrochemical oxygen reduction reaction (ORR), was investigated using cyclic voltammetry (CV) on the electrodeposited manganese oxide (MnO _x )-modified glassy carbon (MnO _x -GC) electrode in the room temperature ionic liquids (RTILs) of EMIBF₄, i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄). The results demonstrated that, after being modified by MnO _x on a GC electrode, the reduction peak current of oxygen was increased to some extent, while the oxidation peak current, corresponding to the oxidation of superoxide anion, i.e., O₂⁻ was attenuated in some degree, suggesting that MnO _x could catalyze ORR in RTILs of EMIBF₄, which is consistent with the results obtained in aqueous solution. To accelerate the electron transfer rate, multi-walled carbon nanotubes (MWCNTs) was modified the GC electrode, and then MnO _x was electrodeposited onto the MWCNTs-modified GC electrode to give rise to a MnO _x /MWCNTs-modified GC electrode, consequently, the improved standard rate constant, k_s, originated from the modified MWCNTs, along with the modification of electrodeposited MnO _x , showed us a satisfactory electrocatalysis for ORR in RTILs of EMIBF₄. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 3, pp. 340–345. The article is published in the original.     

Effect of the Calcination Temperature and Composition of the MnO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>–ZrO<Subscript>2</Subscript> System on Its Structure and Catalytic Properties in a Reaction of Carbon Monoxide Oxidation

The effect of the calcination temperature and composition of the MnO_x–ZrO₂ system on its structural characteristics and catalytic properties in the reaction of CO oxidation was studied. According to X-ray diffraction analysis and H₂ thermo-programmed reduction data, an increase in the calcination temperature of Mn_0.12Zr_0.88O₂ from 450 to 900°C caused a structural transformation of the system accompanied by the disintegration of solid solution with the release of manganese ions from the structure of ZrO₂ and the formation of, initially, highly dispersed MnO_x particles and then a crystallized phase of Mn₃O₄. The dependence of the catalytic activity of MnO_x–ZrO₂ in the reaction of CO oxidation on the calcination temperature takes an extreme form. A maximum activity was observed after heat treatment at 650–700°C, i.e., at limiting temperatures for the occurrence of a solid solution of manganese ions in the cubic modification of ZrO₂. If the manganese content was higher than that in the sample of Mn_0.4Zr_0.6O₂, the phase composition of the system changed: the solid solution phase was supplemented with Mn₂O₃ and β-Mn₃O₄ phases. The samples of Mn_0.4Zr_0.6O₂–Mn_0.6Zr_0.4O₂ exhibited a maximum catalytic activity; this was likely due to the presence of the highly dispersed MnO_x particles, which were not the solid solution constituents, on their surface in addition to an increase in the dispersity of the solid solution.