The effect of cobalt on the activation of fused iron catalyst for ammonia synthesis

BET, scanning electron microscopy, X-ray diffraction, Mössbauer spectroscopy, X-ray fluorescence spectroscopy and McBain thermobalance were used to investigate the effect of cobalt on the reduction behavior and activity of used iron catalyst for ammonia synthesis. Activity tests were carried out under 10 MPa in the 350–450°C temperature rang. Studies were performed on the traditional multipromoted iron catalyst and on the series of catalysts prepared with addition of cobalt. Addition of cobalt promoted the iron catalyst for ammonia synthesis. The most active sample was that containing approx. 5.5% wt Co. Cobalt changed the reduction behavior of the catalyst. The rate of the surface change during reduction was higher for the case of the ‘cobalt catalyst’; however the rate of mass change was higher for a typical iron catalyst. The process of reduction was probably followed by the formation of an Fe₃Co compound and by the surface faceting, with the exposure of an Fe(111) plane.     

Methane decomposition over ceria modified iron catalysts

The catalytic behaviour of ceria supported iron catalysts (Fe–CeO₂) was investigated for methane decomposition. The Fe–CeO₂ catalysts were found to be more active than catalysts based on iron alone. A catalyst composed of 60 wt.% Fe₂O₃ and 40 wt.% CeO₂ gave optimal catalytic activity, and the highest iron metal surface area. The well-dispersed Fe state helped to maintain the active surface area for the reaction. Methane conversion increased when the reaction temperature was increased from 600 to 650 °C. Continuous formation of trace amounts of carbon monoxide was observed during the reaction due to the oxidation of carbonaceous species by high mobility lattice oxygen in the solid solution formed within the catalyst. This could minimise catalyst deactivation caused by carbon deposits and maintain catalyst activity over a longer period of time. The catalyst also produced filamentous carbon that helped to extend the catalyst life.     

Amomax-10/10H氨合成催化剂升温还原理论与实践

从Amomax-10/10H催化理论和生产实践两个维度提炼了Amomax-10/10H氨合成催化剂升温还原过程关键技术。理论方面, 从还原反应的特点可以推导出还原过程的基本还原原则, 从铁比[w（Fe ²⁺）/w（Fe ³⁺）]和铁氧比[n（Fe）/n（O）]角度来推导出了Amomax-10/10H的近似分子式Fe₉O₁₀和Fe₉O;从Fe含量高和O含量低的角度, 分析了Amomax-10/10H具有良好的催化活性之理论依据;从纳米级钝化膜处于热力学亚稳定状态, 解释了Amomax-10H具有优异的低温还原性能, 以及解释了高低搭配、先易后难、分层串联还原的理论依据。实践方面：遵循“二高四低”、“阶梯式”升温、“不同时提温提压”的还原操作原则, 这是稳定升温还原操作、防止水气浓度超标、保证催化剂活性的必要举措。     

Emission of excited potassium species from an industrial iron catalyst for ammonia synthesis

The angular dependence of potassium emission-desorption is studied from a fused iron catalyst of the type used for ammonia synthesis. The excited species (K^*, K _n ^* , etc.) and positive ions K⁺ have strongly different angular distributions. The bilobular distribution measured for ion desorption is concluded to be either due to excited atoms, so-called Rydberg atoms, or excited clusters. Both types of species have to desorb from the edges of the sample and become field ionized and deexcited just outside the sample, as reported in previous studies on an iron oxide catalyst. The peak in the normal direction measured for excited species is due to excited cluster formation outside the catalyst surface. Similarities with previous results for other catalysts are observed. The possibility that the promoter function of potassium in the ammonia synthesis is due to excited species is pointed out.On leave from Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Cracow, Poland.     

Catalytic decomposition of nitrous oxide over Fe-BEA zeolites: Essential components of iron active sites

The catalytic decomposition of N₂O was investigated over Fe-BEA zeolites treated with various methods such as reduction, steaming and dissolution with potassium nitrate and nitric acid solutions in order to deduce the essential components of the active sites for the decomposition. The iron species were characterized by XPS, XANES, ESR, NO adsorption, and linear sweep voltammetry. The reduction-treated Fe-BEA zeolite with the large amounts of Fe(II) and Fe(III) species showed the highest activity. On the contrary, the dissolution treatment with the potassium nitrate solution seriously deteriorated the catalytic activity of the Fe-BEA zeolite by agglomerating iron oxide clusters and interaction between iron and potassium atoms. The catalytic roles of Fe(II)/Fe(III) species and the negative effect of potassium on the catalytic activity of the Fe-BEA zeolites were discussed.     

Hydrogen Production by Catalytic Hydrolysis of Sodium Borohydride with a Bimetallic Solid-State Co-Fe Complex Catalyst

The addition of the active non-noble metal species on a ligand can influence the catalytic performance of catalyst. In the present work, a new bi-metallic solid-state complex catalyst system, including 4-4’-methylene bis(2,6-diethyl) aniline-3,5-di-tert-butylsalisilaldimin ligand and Fe and Co metal salts are prepared for hydrogen generation by catalytic hydrolysis of NaBH₄. It was found that the Co/Fe mixture ratio, temperature, NaBH₄, and NaOH concentrations, all exert considerable influence on the catalytic effectiveness of Co–Fe complex catalyst towards the hydrolysis reaction of NaBH₄. The results suggested that the optimal mixture percentage of Co–Fe complex catalyst is 80:20. The obtained complex catalysts are characterized by XRD, FT-IR, and SEM techniques.     

Iron catalyst for ammonia synthesis doped with lithium oxide

Iron catalysts doped with Al₂O₃, CaO were obtained by melting iron oxide with 2.2 wt.% of Al₂O₃, 2.1 wt.% of CaO. The reduced catalyst was impregnated with lithium hydroxide water solution. Activity measurements were carried out in the laboratory installation in the temperature range 623–773 K under the pressure of 10 MPa. The activity of catalyst containing 0.79 wt.% of Li₂O and reduced at 773 K was similar to the activity of an industrial iron catalyst doped with potassium oxide. After reduction at 923 K the catalyst containing 0.48 wt.% of Li₂O was about 15% more active than the industrial catalyst. Increasing Li₂O concentration results in the decrease of the surface area of a catalyst reduced at 923 K. The most active catalysts doped with lithium oxide were more active than the industrial catalyst when their activity was calculated and scaled down to surface area units.     

Surface structures in ammonia synthesis

Ammonia synthesis is one of the most structure sensitive catalytic reactions. Reaction studies using single crystals showed the open (111) and (211) crystal faces of iron and the and crystal faces of rhenium to be most active, while the close packed iron (110) and rhenium (0001) crystal faces were almost inactive. These studies suggest that seven (C₇) and eight (C₈) metal atom coordinated surface sites, which are available only on the active surfaces, are very active for the dissociation of dinitrogen, the limiting factor in the reaction rate under most experimental circumstances. In this paper, the experimental evidence for the existence of the C₇ sites in iron is reviewed. In addition, the role of potassium in creating a different active site which is less sensitive to the iron surface structure is discussed. Newly developed surface science techniques should permit investigations into the dissociation of dinitrogen at the C₇ sites and how the resulting chemisorbed nitrogen atoms are removed to allow for reaction turnover. Advances in LEED-surface crystallography, allowing detailed determination of relaxation in the clean metal surfaces and adsorbate induced restructuring of the metal surface, reopen the question of the real structure of the active sites in the presence of atomic nitrogen, or atomic nitrogen coadsorbed with potassium and oxygen. Investigation of the dynamics of surface restructuring involving the movements of both the substrate metal atoms and the chemisorbed atoms by surface diffusion becomes feasible by the availability of the high pressure/high temperature STM system built in our laboratory. Studies of the surface structures of the model iron catalysts under dynamic conditions, using 0.1 ms time resolution and atomic spatial resolution under reaction conditions are now possible.     

The role of Fe on PtPd oxidation catalyst prepared by simultaneous and sequential incipient wetnesses

The roles and effects of Fe on the catalytic performance and physicochemical properties of a PtPd diesel oxidation catalyst prepared by three different methods were investigated by CO oxidation reaction, X-ray diffraction, temperature-programmed reduction (TPR), temperature-programmed oxidation, and BET surface area. It was found that the roles of Fe depended strongly on the sequential order of Fe introduction during the preparation of the PtPd catalyst. The Fe/PtPd/Al₂O₃ catalyst was prepared by introducing Fe onto the PtPd/Al₂O₃, and the PtPd/Fe/Al₂O₃ catalyst was obtained by loading the PtPd onto the Fe/Al₂O₃. The former had a superior activity. From the TPR results, the catalytic activity of CO oxidation was correlated with the oxygen mobility of the iron oxides. For PtPd/Fe/Al₂O₃, the iron interacted preferentially with the alumina support forming FeAlO₃, which resulted in the stabilization of the support and a reduction in the surface area. The major role of Fe was to promote the enhancement of the catalytic activity of PtPd through an intimate interaction between the PtPd and iron oxides, which had lattice oxygens to generate oxygen with oxidation abilities.     

Quasi-continuous synthesis of iron single atom catalysts via a microcapsule pyrolysis strategy

Single atom catalysts (SACs), featured with atomically dispersed metal species, have been considered as one of the most promising catalytic materials because of the excellent performance in various high-value-added reactions. However, the large-scale and continuous-type production of such SACs is still challenging. Herein, a novel and facile microcapsule strategy for the quasi-continuous synthesis of iron SACs supported on S, N co-doped carbon (Fe/SNC) is developed, and the Fe species are presented as isolated active sites and stabilized as the FeN₃S-like structure. The as-prepared Fe/SNC catalysts exhibit excellent catalytic properties for selective oxidation of arylalkanes, which followed pseudo-first-order kinetics with an E_a = 41.5 kJ/mol. More importantly, the two Fe/SNC catalysts synthesized at different continuous times showed essentially identical catalyst structure and catalytic performance, demonstrating the superior reliability of our microcapsule strategy for the quasi-continuous production of SACs, which can be easily scaled up to industrial application.     

Introducing trace Co to molybdenum carbide catalyst for efficient ammonia synthesis

Development of the cost-effective catalysts with excellent catalytic performance is highly demanded for ammonia synthesis, and the strong adsorption of ammonia greatly hinders the design of cost-effective and high-performance ammonia synthesis catalysts. Herein, we report that the addition of a small amount of Co species (0.1 wt%) into Mo₂C catalyst, which can provide electrons to Mo₂C, not only leads to improvement of the adsorption and migration of hydrogen, but also facilitates the adsorption and desorption of ammonia. Consequently, Mo₂C catalyst with 0.1 wt%Co offers a 40% higher ammonia synthesis activity and a lower negative reaction order with respect to NH₃ in comparison to Mo₂C. This work stresses the importance of the minor components in improving the ammonia synthesis activity by accelerating the migration of reactants over the catalyst surface and the escape of products from the catalyst.     

Nickel-iron catalysts prepared by homogeneous deposition-precipitation of cyanide complexes on a titania support

Nickel-iron catalysts have been prepared by homogeneous deposition-precipitation of complex nickel-iron cyanides on a titania support. The nickel-iron alloys obtained after calcination and reduction of the cyanide precursors were characterized by Mössbauer spectroscopy, high-temperature X-ray diffraction, and magnetic measurements. Fischer-Tropsch experiments show remarkable results. Catalysts prepared from K₃Fe(CN)₆ and Na₂Fe(CN)₅NO cyanide precursors exhibit a high activity and selectivity, whereas catalysts prepared from K₄Fe(CN)₆ do not show any activity. This lack of activity is caused by the presence of potassium in catalysts prepared from K₄Fe(CN)₆. Potassium or iron titanate inhibits the adsorption of CO on the nickel-iron surface. Deactivation of active nickel-iron catalysts was caused by the deposition of inactive carbon during Fischer-Tropsch synthesis.     

Nanostructured Pt-M/C (M = Fe and Co) catalysts prepared by a microemulsion method for oxygen reduction in proton exchange membrane fuel cells

Nanostructured Pt-M/C (M = Fe and Co) catalysts have been synthesized by a microemulsion method and a high-temperature route. They have been characterized by cyclic voltammetry in 1 M H₂SO₄ and for oxygen reduction in proton exchange membrane fuel cells (PEMFC). The Pt-M alloy catalysts synthesized by the microemulsion method show higher electrochemical active surface area than those prepared by the high-temperature route, and some of them exhibit improved catalytic activity towards oxygen reduction compared to pure Pt. Among the various alloy catalysts investigated, the Pt-Co/C catalyst prepared by the microemulsion method shows the best performance with the maximum catalytic activity and minimum polarization loss. Mild heat treatment of the catalysts prepared by the microemulsion method at moderate temperatures (200 °C) in reducing atmosphere is found to improve the catalytic activity due to a cleaning of the surface and an increase in the electrochemical surface area.     

钌基氨合成催化剂氢氮吸附性能的研究

The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispers     

Potassium-Promoted Carbon-Based Iron Catalyst for Ammonia Synthesis. Effect of Fe Dispersion

Potassium-promoted iron catalysts supported on thermally modified, partly graphitized carbon were studied in the ammonia synthesis reaction. Iron nitrate was used as a precursor of the active phase and KOH or KNO₃ were used as promoters. The kinetic studies of NH₃ synthesis were carried out in a differential reactor under 63 bar and 90 bar pressure. Hydrogen chemisorption, X-ray diffraction and transmission electron microscopy experiments were performed to determine the dispersion of iron in the specimens. All the K⁺–Fe/C catalysts proved to be sensitive to ammonia, the NH₃ partial pressure dependencies of their reaction rates being close to that of the commercial magnetite catalyst (KM I, H. Topsoe). The catalytic properties of the promoted Fe particles on carbon were shown to be dependent upon the iron dispersion, i.e. smaller particles exhibited higher turnover frequency in NH₃ synthesis. It is suggested that either small Fe crystallites expose more highly active sites, e.g. C-7 (B-5) or the promotion of small crystallites by the alkali is more efficient.     

熔铁氨合成催化剂中钾组分的水溶性及其对催化活性的作用

报道了浸水处理后高强度A110－5Q球形氨合成催化剂各种物理化学性能的变化考察了两种铁酸钾KFeO_2、K_1＋x_Fe_11o_17（x＝o～1）的水溶性对溶铁氨合成催化剂（氧化态）中存在的水溶性钾和非水溶性钾进行了归属水溶性钾主要集中在Fe_3O_4晶粒间的边界上,以KFeO_2、KOH、K_2CO_3和KAlO_2等物相存在;非水溶性钾则是高度分散于Fe_3O_4晶粒内的非计量化合物K_1+x_Fe_11O_17（x＝0～1）水溶性钾量远高于非水溶性钾的含量,但前者对催化活性的作用却不如后者明显,对这一现象的本质原因进行了深入的探讨。     

制备方法对Co-Pd/TiO2催化剂催化CH4-CO2梯阶转化的影响

以钴、钯为活性金属, 分别采用浸渍法和溶胶-凝胶法制备了Co-Pd/TiO₂催化剂, 考察了不同制备方法制备的Co-Pd/TiO₂催化剂对CH₄-CO₂梯阶转化直接合成C₂含氧化合物的影响。利用XRD、XPS和N₂-吸附-脱附对催化剂进行了表征。结果表明:两种方法制备的催化剂反应前与反应后表面织构都存在较大变化, 且催化剂中均存在CoTiO₃物种, 这是活性金属Co与载体TiO₂之间发生强相互作用, CO²⁺替代TiO₂晶格中的Ti⁴⁺的结果;CoO和金属Pd可能是该反应的活性中心;反应前与反应后溶胶-凝胶法制备的催化剂的表面Co含量均低于浸渍法制备的催化剂, 而表面Pd含量则均高于浸渍法制备的催化剂, 且溶胶-凝胶法制备的催化剂各种产物的生成速率均高于浸渍法制备的催化剂, 因此, 与浸渍法制备的催化剂相比, 溶胶-凝胶法制备的催化剂具有更好的催化活性。     

铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢性能研究

采用浸渍-还原法制备了铁、钴、镍、铜和锌催化剂,考察了其催化氨硼烷水解产氢性能,并优化了钴催化剂的制备条件和反应条件。结果发现,铁催化剂中铁以Fe₂B合金相存在,钴催化剂中钴以金属钴存在,镍催化剂中镍以金属镍和Ni（OH）₂·2H₂O存在,铜催化剂中铜以金属铜和氧化亚铜存在,锌催化剂中锌以Zn₄SO₄（OH）₆·4H₂O存在。铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢活性由大到小顺序为钴催化剂、镍催化剂、铜催化剂、铁催化剂、锌催化剂。显然,具有金属钴相的钴催化剂、金属镍相的镍催化剂和金属铜相的铜催化剂催化氨硼烷产氢活性高于具有Fe₂B合金相的铁催化剂。锌催化剂在制备条件下不能被还原为金属相,它几乎没有催化氨硼烷产氢活性。氯化钴与还原剂硼氢化钠的物质的量比为1∶1.3、还原温度为303 K时制备的钴催化剂催化BH₃NH₃水解产氢性能最佳。反应动力学计算表明钴催化剂催化BH₃NH₃水解产氢反应对氨硼烷浓度的反应级数为零级,对钴催化剂浓度的反应级数为一级,活化能为58 kJ/mol。     

熔铁催化剂活性与其母体铁氧化物形态和组成的关系(Ⅱ) 表面活性位和氨合成反应速率

采用N2 低温吸附、CO和CO2 化学吸附技术和活性试验研究了不同铁氧化物为母体的氨合成催化剂表面活性位与催化活性的关系 .结果表明 ,活性相铁原子在表面的暴露百分数 <1 % ,99%以上的铁原子掩埋在体相内部 .随着母体铁氧化物性质和组成的变化 ,催化剂活性 (以氨的体积分数表征 )、质量反应速率 (rm)、合成氨转换频率 (TOF)和表面酸覆盖度 (SA)及其酸碱覆盖度的比例 (SA/SK)有相似的变化规律 ,即与Fe2 +/Fe3+呈驼峰形变化曲线 .实验发现 ,随着母体中FeO含量的增加 ,还原后催化剂表面性质和表面结构改变 ,表面活性位数目减少而活性位强度增大 .这可能是结构改性剂Al2 O3对Fe晶面的表面重构作用所致 .     

On the formation of cobalt–molybdenum sulfides in silica‐supported hydrotreating model catalysts

Model catalysts, consisting of a conducting substrate with a thin SiO₂ layer on top of which the active catalytic phase is deposited by spincoating impregnation, were applied to study the formation of the active CoMoS phase in HDS catalysts. The catalysts thus prepared showed representative activity in the hydrodesulfurization of thiophene, confirming that these models of HDS catalysts are realistic. Combination of the sulfidation behaviour of Co and Mo studied by XPS and activity measurements shows that the key in the formation of the CoMoS phase is the retardation of the sulfidation of Co. Complexing Co to nitrilotriacetic acid complexes retarded the Co sulfidation, resulting in the most active catalyst. Due to the retardation of Co in these catalysts, the sulfidation of Mo precedes that of Co, thereby creating the ideal conditions for CoMoS formation. In the CoMo catalyst without NTA the sulfidation of Co is also retarded due to a Co–Mo interaction. However, the sulfidation of Mo still lags behind that of Co, resulting in less active phase and a lower activity in thiophene HDS. This revised version was published online in June 2006 with corrections to the Cover Date.