Role of manganese oxide octahedral molecular sieves in styrene epoxidation

Manganese oxide octahedral molecular sieves having 2 x 2 tunnel structure (OMS-2) and synthesized by different methods were used for studying styrene oxidation with tert-butyl hydroperoxide (TBHP) as the oxidant. The catalytic activity of the as-synthesized OMS-2 materials was investigated. The physical and chemical properties of the OMS-2 materials are related to their activity in styrene oxidation. This particular study emphasizes the acid-base properties and the porous nature of these materials, and their role in styrene oxidation. Results of styrene oxidation reveal that acidity coupled with high porosity play a crucial role in these catalytic reactions. A desired acidity coupled with pore volume found in OMS-2 synthesized by reflux methods (OMS-2(R)) and high-temperature methods (OMS-2(HT)) produces materials with higher styrene conversion and styrene oxide selectivity when compared with OMS-2 synthesized by solvent free (OMS-2(S)), microwave (OMS-2(MW)), or hydrothermal methods (OMS-2(HY)). Transition metal doped OMS-2 catalysts show better selectivity of styrene oxide when compared to their undoped catalysts.     

掺Ag对氧化锰八面体分子筛催化CO氧化性能的影响

采用回流法在酸性介质中合成了掺杂贵金属Ag的氧化锰八面体分子筛(OMS-2).利用X射线衍射、低温N2吸附、透射电子显微镜及程序升温脱附(TPD)等技术对固体材料的结构进行了表征,考察了材料对CO氧化反应的催化性能,以及Ag的掺杂对该反应的影响.结果表明,合成的OMS-2材料属于cryptomelane一维隧道结构,适量Ag的掺杂使分子筛的有序性得到改善,孔径更均一.Ag的加入还能明显提高催化剂的反应活性.O2-TPD和CO-TPD实验表明,Ag的引入使材料对CO的吸附性能及晶格氧的扩散能力得到显著增强,这是提高催化剂对CO氧化催化能力的主要原因.     

Pd/SAPO-34催化剂上CO低温氧化反应

 采用水热法合成了小晶粒的 SAPO-34, MnSAPO-34 和 CuSAPO-34 分子筛, 并以它们为载体采用浸渍法制备了一系列不同 Pd 含量的催化剂用于催化 CO 氧化反应. 结果表明: 分子筛载体、催化剂制备条件、反应条件、Pd 含量及预还原等对催化剂的活性影响较大. 催化剂活性随焙烧温度的增加而降低, 而随着反应温度的升高而提高, 担载在 SAPO-34 上 Pd 含量为 1.35% 时性能最佳. X射线衍射和透射电镜结果表明 Pd 物种高度分散于催化剂上, 粒子粒径在 2~8 nm; X射线光电子能谱及氢气程序升温还原结果表明, 高度分散的 Pd2+ 物种是 CO 氧化反应活性位. 随着反应进行被还原为 Pd0 物种, 因而导致催化剂活性下降. H2 预还原处理催化剂致使活性下降的实验结果也支持了这一结论.     

Effects of reduction temperature and content of Pd loading on the performance Pd/CeO2 catalyst for CO oxidation

Palladium nanoparticles were prepared by thermally assisted reduction using glutathione as reduction agent. The Pd loading on CeO₂ for CO oxidation was optimized to 1.5 wt%. The catalysts reduced at 350 C show the highest activity for CO oxidation, which achieve 100% CO conversion at 70℃.     

Pd-Cu/羟磷灰石的制备及常温常湿CO催化氧化性能

通过溶胶-凝胶法(SG)和水热法(HT)合成了羟磷灰石载体(HAP-SG, HAP-HT), 以浸渍法制备负载型Pd-Cu/HAP催化剂(PC-SG, PC-HT), 并考察其常温常湿条件下CO催化氧化反应性能. 采用电感耦合等离子体发射光谱(ICP-OES)、 N₂物理吸附-脱附、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 H₂程序升温还原(H₂-TPR)、 CO₂程序升温脱附(CO₂-TPD)、 X射线光电子能谱(XPS)和CO原位漫反射傅里叶变换红外光谱(in-situ DRIFTS)等手段对Pd-Cu/HAP催化剂进行了表征. 结果表明, 相比于PC-SG, PC-HT具有较大比表面积和孔容, 含有较多的Cu₂Cl(OH)₃物种且与Pd物种和载体直接产生了较强的相互作用; 而且PC-HT表面含有较强CO活化能力的Pd⁺物种和更多具有较强氧化还原性质的Cu⁺物种, 以及较少数量和较低强度的碱性位点, 因而表现出更加优异的常温常湿条件下CO催化氧化性能.     

Effects of precipitants and surfactants on catalytic activity of Pd/CeO<Subscript>2</Subscript> for CO oxidation

A series of precipitants and commercial surfactants (soft templates) were employed to synthesize mesoporous/nano CeO₂ by a hydrothermal method. As-prepared CeO₂ was impregnated with palladium and employed for low-temperature catalytic oxidation of CO. It was found that both soft templates and precipitants had significant effects on the morphology, particle size, crystallinity, and porous structure of the CeO₂, having a significant effect on the surface palladium abundance, molar ratios of surface species, and catalytic activity of the final impregnated Pd/CeO₂. Using ammonia as precipitant could facilitate increased surface palladium abundance and surface molar ratios of PdO/Pd _SMSI , Ce³⁺/(Ce³⁺ + Ce⁴⁺), and O_surface/O_lattice. The catalytic activity of the final Pd/CeO₂ catalysts could be enhanced as well. The optimal P123-assisted ammonia-precipitated Pd/CeO₂ catalyst exhibited over 99% catalytic conversion of CO at 50 °C.     

双介孔硅基材料负载Pd催化剂上甲苯氧化性能的研究

催化氧化技术是挥发性有机物(VOCs)减排与控制的主流技术之一,其关键之处在于高效催化材料的研究与开发,负载型贵金属催化材料由于其低温下优越的VOCs催化氧化性能,受到国内外研究者的广泛关注.对于负载型催化剂而言,载体的性质直接影响活性相的分散,反应物和生成物的扩散与吸脱附,是影响负载型催化剂性能的主要因素.近年来,多级孔结构硅基材料由于具有多级的孔道结构、高比表面积和大的孔体积,逐渐成为VOCs催化氧化材料的研究热点.本文采用溶胶凝胶法和浸渍法制备了系列双介孔结构硅基材料负载Pd催化剂(Pd/BMS-x),通过控制合成过程中氨水的用量以调节催化剂的介孔结构分布. X射线衍射(XRD)结果表明,所合成的Pd/BMS-x催化剂在~2.0°的衍射峰,类似于MCM-41的(100)晶面衍射峰,表明所有的样品均具有有序的介孔结构. N2吸脱附实验表明所有样品的比表面积均高于1000m2/g,孔径分布表明Pd/BMS-30样品为单一介孔结构,而Pd/BMS-5~Pd/BMS-20样品具有2.64 nm以及18–45 nm范围内的双介孔结构,且Pd/BMS-15样品介孔分布较为集中. Pd/BMS-x催化剂上甲苯催化氧化性能测试表明,双介孔结构的Pd/BMS-5~Pd/BMS-20催化剂上甲苯催化氧化活性远高于单一介孔结构的Pd/BMS-30催化剂,表明载体结构对催化剂性能有重要影响.其中, Pd/BMS-15催化剂性能最佳(T90为228°C)且具有较强的稳定性,250°C条件下,反应持续60h催化剂未见明显失活. SEM和TEM结果表明, Pd/BMS-15催化剂中Pd高度分散于载体上,平均粒径在~3 nm左右.而Pd/BMS-30催化剂中Pd颗粒间有明显的团聚,平均粒径在8~17 nm之间.分散度测试表明,单一介孔结构的Pd/BMS-30催化剂, Pd分散度仅为27%,而双介孔结构Pd/BMS-5–Pd/BMS-20催化剂介于39%到69%,其中Pd/BMS-15催化剂中Pd分散度高达69%.与常规单一介孔MCM-41和MCM-48负载Pd催化剂相比,在低空速(42000 h–1)条件下, Pd/BMS-15催化剂上甲苯催化氧化性能与Pd/MCM-41和Pd/MCM-48催化剂相当.高空速(70000h–1)条件下, Pd/BMS-15催化剂的活性远高于单一介孔的Pd/MCM-41和Pd/MCM-48催化剂. Pd/BMS-15催化剂独特的双介孔结构,有利于活性相Pd的分散、反应物的扩散和传输,特别是在高空速条件下,有利于反应物与活性相的接触,提高了材料的氧化反应性能.进一步考察了材料的水热稳定性,将11 vol%的水蒸气引入到反应体系中,测试结果表明水蒸气的加入导致Pd/MCM-41和Pd/MCM-48催化剂的甲苯催化氧化性能显著下降,反应500 min后甲苯转化率分别从100%下降到76%和81%,而对于Pd/BMS-15催化剂,水蒸气的引入并未导致其活性明显下降,从而表明Pd/BMS-15催化材料具有较高的水热稳定性.     

Low temperature carbon monoxide catalytic oxidation at the Pd/Ce–Zr–Al–Ox catalyst

The homogeneous chemical composition ceria–zirconia–alumina (Ce–Zr–Al–O_x) nano-alloy were successfully synthesized by surfactant-assisted parallel flow co-precipitation method and applied as supports for low temperature CO oxidation. The experiment conditions were studied in detailed. At 0.92 wt% Pd loading, 30,000 ppm CO could be completely oxidized to CO₂ at 30 °C at a WHSV of 4,380 ml g^?1 h^?1 over the Pd/Ce–Zr–Al–O_x (n_Ce:n_Zr = 3:1) catalyst. Pd/Ce–Zr–Al–O_x catalysts were systematical studied by mean of BET, XRD and TEM analysis. XRD characterization showed that zirconium element entered into cubic structure of ceria and leaded to structure distortion. Addition of aluminum increased specific surface area of ceria–zirconia solid solution substantially. The average pore diameter of Ce–Zr–Al–O_x support palladium catalysts were the key impact factor for CO oxidation. When the Pd/Ce–Zr–Al–O_x catalysts had highly dispersed palladium nanoparticles, large average pore diameter, suitable surface area and pore volume, the activity of CO oxidation was the best.     

Pd nanoparticles immobilized on boehmite by using tannic acid as structure-directing agent and stabilizer: a high performance catalyst for hydrogenation of olefins

Boehmite-supported Pd nanoparticles (Pd–TA–boehmite) were successfully synthesized by a hydrothermal method using tannic acid as the structure-directing agent as well as stabilizer. The physicochemical properties of the Pd–TA–boehmite catalyst were well characterized by XPS, XRD, N₂ adsorption/desorption, and TEM analyses. Catalytic hydrogenation of olefins was used as the probe reaction to evaluate the activity of the Pd–TA–boehmite catalyst. For comparison, the Pd–boehmite catalyst prepared without tannic acid was also employed for olefin hydrogenation. For all the investigated substrates, the Pd–TA–boehmite catalyst exhibited superior catalytic performance than the Pd–boehmite catalyst. For the example of hydrogenation of allyl alcohol, the initial hydrogenation rate and selectivity of the Pd–TA–boehmite catalyst were 23,520 mol/mol h and 99 %, respectively, while those of the Pd–boehmite catalyst were only 14,186 mol/mol h and 93 %, respectively. Additionally, the hydrogenation rate of the Pd–TA–boehmite catalyst could still reach 20,791 mol/mol h at the 7th cycle, which was much higher than that of the Pd–boehmite catalyst (5,250 mol/mol h) at the 4th cycle, thus showing an improved reusability.     

负载型Cu-Pd双金属纳米氧化物催化剂催化合成碳酸二乙酯：Cu（I）作为活性中心

催化反应活性与催化剂活性组分的存在价态密切相关,所以探讨催化剂在反应过程中的活性中心及其价态变化,对于催化反应机理和催化剂的研究都显得十分重要.目前对于氧化羰基合成碳酸二甲酯催化剂的机理的探讨很多,主要存在的争议是Cu+还是Cu2+作为活性中心,以及铜物种的配位状态.大多体系都是以分子筛为载体的铜基催化剂,其活性中心的研究存在铜离子在分子筛中的定位问题,而且催化活性也会受到分子筛结构的影响.采用这种方法研究活性中心的影响因素较多,存在一定的局限性.因此,直接制备纳米级的铜基氧化物用于本催化体系,有利于更直观简单地探索其活性中心.纳米级金属氧化物材料是一种新型的功能性材料,而纳米铜基氧化物(CuO和Cu2O)因其独特的物化性质和结构而引起广泛关注.我们采用水热法制备纳米CuO及其它氧化物,研究了NaOH浓度对催化剂的催化性能的影响;葡萄糖是一种还原性较强的还原剂,其用量必定会对所制备的氧化物的物种有所影响.为了探究Cu0和Cu+在本体系中的作用,采用不同葡萄糖用量制备了具有不同Cu2O含量的PdCl2/Cu-Cu2O催化剂.在上述研究基础上,我们采用X射线衍射、场发射扫描电子显微镜、热重分析、等离子体原子发射光谱等表征手段研究了负载型纳米铜基氧化物催化剂在合成碳酸二乙酯反应中催化性能差异的原因,旨在直接考察活性中心主要是Cu+还是Cu2+,避免分子筛等体系中载体结构的影响,研究结果更具参考性.结果发现, NaOH浓度为5 mol/L时制备的PdCl2/CuO和PdCl2/Cu-Cu2O催化剂的性能优于其他浓度下制备的催化剂,这可能是由于不同浓度的碱溶液会对铜离子的沉淀过程产生不同的影响;相同NaOH浓度下制备的催化剂中, PdCl2/Cu-Cu2O催化剂的催化性能明显优于PdCl2/CuO催化剂,这可能是由于PdCl2/Cu-Cu2O催化剂更有利于反应过程中电子的传递,从而表现出更好的催化性能,我们推测Cu0和Cu+可能更有利催化乙醇氧化羰基合成DEC;表征分析发现PdCl2/CuO和PdCl2/Cu-Cu2O均具有很好的热稳定性,两种催化剂中PdCl2负载量几乎相同,因此,主要影响催化性能的因素是载体CuO和Cu-Cu2O中铜的价态.采用不同葡萄糖用量制备了含有不同Cu2O含量的PdCl2/Cu-Cu2O催化剂,其中, PdCl2/Cu-Cu2O-2催化剂中含有更多的Cu2O,在反应中乙醇转化率达到了7.2%, DEC的选择性为97.9%, DEC的时空收率可达到151.9 mg·g–1·h–1.由此可见在乙醇气相氧化羰基合成DEC体系中, Cu+是主要的活性中心.     

Au/TiO2 nanotube catalysts prepared by combining sol–gel method with hydrothermal treatment and their catalytic properties for CO oxidation

A new preparation method for Au/TiO₂ nanotubes (NTs) by combing sol–gel with hydrothermal treatment technique was developed. The TiO₂ NTs calcined at 300 °C were nearly uniform, and the gold particles were distributed homogeneously. The possible formation mechanism was suggested. The 5 % Au/TiO₂ NTs calcined at 300 °C had the best catalytic activity for CO oxidation, and their conversion of CO remained at 100 % during 60 h on stream. This preparation method could improve the thermal stability of Au/TiO₂ nanotube catalysts.     

有机高分子固载钯催化剂的羰基化和加氢催化性能

本文利用耐温性能较好的主链上含有多个配位原子(N,O)能成膜的直链高分子杂环联苯聚醚酮(PEK),带酚酞侧基的聚醚砜(PES-C)和两种聚酰亚胺(PCK和PIK)为载体固载PdCl~2,制备了高分子固载钯催化剂。研究了它们在烯丙基溴的常压羰基化反应和1-辛烯的常压加氢反应中的催化性能。考察了催化剂的制备方法、Pd含量、溶剂和高分子的主链结构对催化剂活性的影响。催化剂Pd-PEK(Ⅰ) (Pd wt%=0.22%)和Pd-PES-C(Ⅱ)(Pd wt%=0.28%)在温和的条件下对上述两反应都表现出了很高的催化活性。在极低的Pd含量(Pd wt%=0.04%)时,催化剂Pd-PES-C(Ⅲ)显示出了特别高的初活性,TOF~m~a~x分别达345mol CO/mol Pd·min和493mol H~2/mol Pd·min。实验结果表明制备方法等因素对催化剂的活性有很大的影响。     

Characterization of trimetallic Pt-Pd-Au/CeO2 catalysts combinatorial designed for methane total oxidation

In the present work, the role and the effect of platinum and gold on the catalytic performance of ceria supported tri-metallic Pt-Pd-Au catalysts have been studied. The optimum composition of these tri-metallic supported catalysts has been discovered using methods and tools of combinatorial catalyst library design. Detailed catalytic, spectroscopic and physico-chemical characterization of catalysts in the vicinity of the optimum in the given compositional space has been performed. The temperature-programmed oxidation of methane revealed that the addition of Pt and Au to Pd/CeO2 catalyst resulted in higher conversion values in the whole investigated temperature range compared to the monometallic Pd catalyst. The time-on-stream experiments provided further evidence for the high-stability of tri-metallic catalysts compared to the monometallic one. Kinetic studies revealed the stronger adsorption of methane on Pt-Pd/CeO2 catalysts than over Pd/CeO2. XPS analysis showed that Pt and Au stabilize Pd in a more reduced form even under condition of methane oxidation. FTIR spectroscopy of adsorbed CO and hydrogen TPD measurements provided indirect evidences for alloying of Pt and Au with Pd. CO chemisorption data indicated that tri-metallic catalysts have increased accessible metallic surface area. It is suggested that advantageous catalytic properties of tri-metallic Pt-Au-Pd/CeO2 catalysts compared to the monometallic one can be attributed to (i) suppression of the formation of ionic forms of Pd(II), (ii) reaching an optimum ratio between Pd0 and PdO species, and (iii) stabilization of Pd in high dispersion. The results also indicate that Pd0 - PdO ensemble sites are required for methane activation.     

CO在Pd平板与Pd38团簇表面上的催化氧化机理研究

采用密度泛函理论(DFT)计算模拟Pd平板和Pd_(38)团簇上的CO催化氧化过程,分析了CO在Pd催化剂表面上的氧化反应机理。结果表明,在Pd_(38)团簇模型上CO催化氧化的决速步骤是O_2的解离,反应能垒为0.65 eV,而在Pd平板模型上的决速步骤是CO的氧化,其反应能垒为0.87 eV。对比决速步骤的活化能发现,CO在Pd_(38)团簇上的氧化反应更易进行,说明CO氧化更易在小颗粒催化剂表面上进行,即Pd催化剂的活性与活性组分颗粒大小相关,活性组分颗粒越小,暴露的活性位点越多,其催化活性也越高。     

On the Catalytic Performance of (ZrO)n (n=1–4) Clusters for CO Oxidation: A DFT Study

The unique characteristic of superatoms to show chemical properties like those of individual atoms opens a new avenue towards replacing noble metals as catalysts. Given the similar electronic structures of the ZrO superatom and the Pd atom, the CO oxidation mechanisms catalysed by (ZrO)_n (n=1–4) clusters were investigated in detail to evaluate their catalytic performance. Our results reveal that a single ZrO superatom exhibits superior catalytic ability in CO oxidation than both larger (ZrO)_n (n=2–4) clusters and a Pd atom, indicating the promising potential of ZrO as a “single-superatom catalyst”. Moreover, the mechanism of CO oxidation catalysed by ZrO^+/− suggests that depositing a ZrO superatom onto the electron-rich substrates is a better choice for practical catalysis application. Accordingly, a graphene nanosheet (coronene) was chosen as a representative substrate for ZrO and Pd to assess their catalytic performances in CO oxidation. Acting as an “electron sponge”, this carbon substrate can both donate and accept charges in different reaction steps, enabling the supported ZrO to achieve enhanced catalytic performance in this process with a low energy barrier of 19.63 kcal/mol. This paper presents a new realization on the catalytic performance of Pd-like superatom in CO oxidation, which could increase the interests in exploring noble metal-like superatoms as efficient catalysts for various reactions.     

Cu含量对Pd-Cu/铝土矿CO氧化催化剂结构和性能的影响

利用资源丰富的天然铝土矿经NaOH溶液水热处理后焙烧,获得比表面积达174 m²·g^-1铝土矿载体,制备了双金属Pd-Cu为活性组分的催化剂,金属Pd负载量为0.5%（质量百分数）,以CO氧化反应为探针反应,详细考察了Cu含量的变化对催化剂物化性能的影响。研究发现,Cu的引入有利于提高金属Pd的分散度,同时随着Cu含量的变化,金属Pd与Cu之间以及金属与铝土矿载体之间的相互作用随之改变。催化剂的CO氧化反应性能评价结果表明,Pd和Cu负载量分别为0.5%和4%的样品（PdCu₄/MB）催化反应性能最佳。结合表征结果认为,PdCu₄/MB的高活性归因于良好的Pd和Cu分散度,金属Pd、Cu以及金属与载体之间较强的相互作用。此外,CO-TPD表征结果说明较强的CO吸附能力和从载体中获取氧的能力也有利于提高PdCu₄/MB样品的CO氧化反应性能。     

Cu含量对Pd-Cu/铝土矿CO氧化催化剂结构和性能的影响

利用资源丰富的天然铝土矿经NaOH溶液水热处理后焙烧,获得比表面积达174 m²·g^-1铝土矿载体,制备了双金属Pd-Cu为活性组分的催化剂,金属Pd负载量为0.5%（质量百分数）,以CO氧化反应为探针反应,详细考察了Cu含量的变化对催化剂物化性能的影响。研究发现,Cu的引入有利于提高金属Pd的分散度,同时随着Cu含量的变化,金属Pd与Cu之间以及金属与铝土矿载体之间的相互作用随之改变。催化剂的CO氧化反应性能评价结果表明,Pd和Cu负载量分别为0.5%和4%的样品（PdCu₄/MB）催化反应性能最佳。结合表征结果认为,PdCu₄/MB的高活性归因于良好的Pd和Cu分散度,金属Pd、Cu以及金属与载体之间较强的相互作用。此外,CO-TPD表征结果说明较强的CO吸附能力和从载体中获取氧的能力也有利于提高PdCu₄/MB样品的CO氧化反应性能。     

柴油尾气DOC催化剂Pt-Pd/CeO2的活性和抗硫性

采用浸渍法制备了不同Pt、Pd比例的Pt-Pd/CeO₂催化剂,考察了其催化氧化模拟柴油车尾气的活性,并测试了抗硫性。活性测试结果表明,Pt、Pd协同降低了催化剂的起燃温度,其比例对催化剂性能影响很大,其中,Pt_0.2Pd_0.8/CeO₂催化剂在模拟柴油车尾气(丙烯(C₃H₆)、一氧化碳(CO)和一氧化氮(NO))中的催化活性最高;C₃H₆的t₅₀降到170℃,CO的t₅₀降到了150℃,显示了良好的Pt、Pd协同效应;H₂-TPR表征和抗硫性结果分析表明,高比例Pt/Pd催化剂具有更多的表面活性氧,其相对数值与催化剂抗硫性能的关联度高,在催化剂硫酸盐中毒的条件下,更有利于催化反应的进行。     

Low-temperature oxidation of carbon monoxide over (Mn1 − x M x )O2 (M = Co, Pd) catalysts

(Mn_{1 ? x} M _x )O₂ (M = Co, Pd) materials synthesized under hydrothermal conditions and dried at 80°C have been characterized by X-ray diffraction, diffuse reflectance spectroscopy, electron microscopy, X-ray photoelectron spectroscopy, and adsorption and have been tested in CO oxidation under CO + O₂ TPR conditions and under isothermal conditions at room temperature in the absence and presence of water vapor. The synthesized materials have the tunnel structure of cryptomelane irrespective of the promoter nature and content. Their specific surface area is 110–120 m²/g. MnO₂ is morphologically uniform, and the introduction of cobalt or palladium into this oxide disrupts its uniformity and causes the formation of more or less crystallized aggregates varying in size. The (Mn,Pd)O₂ composition contains Pd metal, which is in contact with the MnO₂-based oxide phase. The average size of the palladium particles is no larger than 12 nm. The initial activity of the materials in CO oxidation, which was estimated in terms of the 10% CO conversion temperature, increases in the following order: MnO₂ (100°C) < (Mn,Co)O₂ (98°C) < (Mn,Co,Pd)O₂ (23°C) < (Mn,Pd)O₂ (?12°C). The high activity of (Mn,Pd)O₂ is due to its surface containing palladium in two states, namely, oxidized palladium (interaction phase) palladium metal (clusters). The latter are mainly dispersed in the MnO₂ matrix. This catalyst is effective in CO oxidation even at room temperature when there is no water vapor in the reaction mixture, but it is inactive in the presence of water vapor. Water vapor causes partial reduction of Mn⁴⁺ ions and an increase in the proportion of palladium metal clusters.     

Shape-controlled synthesis of manganese oxide octahedral molecular sieve three-dimensional nanostructures

Cryptomelane-type manganese oxide octahedral molecular (OMS) sieve three-dimensional (3D) nanostructures were synthesized via facile temple-free low-temperature hydrothermal reactions. Morphologies of the cryptomelane-type OMS-2 nanoparticles with tunnel dimension of 4.6 x 4.6 A can be tuned by varying reaction temperatures. At low temperature (120 degrees C), OMS-2 dendritic nanoclusters composed of uniform single-crystal nanotetragonal prisms with square cross-sections were formed. At high temperature (180 degrees C), the morphologies of OMS-2 became spherical dandelion-like microspheres composed of uniform single-crystal OMS-2 nanoneedles. Slow oxidation of Mn(2+) by Cr(2)O(7)(-) under hydrothermal conditions is critical for the formation of the hierarchically ordered OMS-2 3D nanostructures.