Phlogophites intercalated with Al2O3 pillars and modified with transition metals as catalysts of the DeNOx process

Natural phlogophite, pre-treated with acids and intercalated with alumina pillars, was used as catalytic support. Transition metals (Fe, Cu) were deposited on the surface of the modified clay materials by an ion-exchange method. The obtained samples were characterized with respect to structure (XRD), texture (BET), composition (EPMA) and chemical nature of the deposited transition metals species (UV-vis-DRS). The phlogophite based materials have been found to be active and selective catalysts of the DeNOx process. The Fe-containing samples were catalytically active at lower temperatures than the clays modified with copper. A competitive ammonia oxidation by oxygen decreased the effectiveness of the DeNOx process in the high temperature range.     

Sn0.5Ti0.5O2催化剂上SO2、NO和CO反应的机理

Sn0.5Ti0.5O2催化剂对NO＋CO反应活性不高， 350 ℃时NO的转化率只有50％,但反应气中含有SO2时， NO的转化率接近100％,说明SO2对Sn0.5Ti0.5O2催化剂上的NO＋CO反应具有促进作用. XPS表征发现,SO2＋CO、SO2＋NO＋CO反应后催化剂表面有微量硫存在，而反应前没有检测到硫的存在.结合反应性能测定、瞬变应答实验、XRD、TPD研究等，发现催化剂上的表面硫参与了NO的催化还原反应，是NO＋CO反应更重要的活性中心.据此，提出了SO2＋NO＋CO反应的氧化还原反应机理.     

The Active Sites of a Rod‐Shaped Hollandite DeNOx Catalyst

The identification of catalytically active sites (CASs) in heterogeneous catalysis is of vital importance to design and develop improved catalysts, but remains a great challenge. The CASs have been identified in the low‐temperature selective catalytic reduction of nitrogen oxides by ammonia (SCR) over a hollandite manganese oxide (HMO) catalyst with a rod‐shaped morphology and one‐dimensional tunnels. Electron microscopy and synchrotron X‐ray diffraction determine the surface and crystal structures of the one‐dimensional HMO rods closed by {100} side facets and {001} top facets. A combination of X‐ray absorption spectra, molecular probes with potassium and nitric oxide, and catalytic tests reveals that the CASs are located on the {100} side facets of the HMO rods rather than on the top facets or in the tunnels, and hence semi‐tunnel structural motifs on the {100} facets are evidenced to be the CASs of the SCR reaction. This work paves the way to further investigate the intrinsic mechanisms of SCR reactions.     

Fe-Cu/ZSM-5催化剂的NH_3-SCR脱硝性能

通过浸渍法制备了Fe和Cu含量比不同的系列Fe-Cu/ZSM-5催化剂,利用XRD、H2-TPR、NH3-TPD和原位DRIFTS等技术对催化剂进行了表征,并对其NH3-SCR脱硝性能进行了研究。结果表明,双金属改性的Fe-Cu/ZSM-5催化剂活性温度窗口拓宽,其中,Fe-Cu/ZSM-5 1∶4催化剂脱硝性能优异,250-450℃下脱硝效率均超过90%,335℃时脱硝效率达到最大值96.46%。铜和铁物种能以无定型氧化物良好分散于载体表面,双金属负载改性催化剂保留了ZSM-5的晶体结构。Fe-Cu/ZSM-5 1∶4催化剂具备丰富的酸性位、良好的氧化还原性能,一定温度条件下NH3-SCR反应过程中同时存在E-R机理和L-H机理,且E-R机理反应起始温度低于L-H机理;200℃为催化脱硝反应的起活温度。     

The catalytic reduction of NO by H2 on Ru(0 0 0 1): Observation of NHads species

Adsorption of NO and the reaction between NO and H₂ were investigated on the Ru(0 0 0 1) surface by X-ray photoelectron spectroscopy (XPS). Surface composition was measured after NO adsorption and after the selective catalytic reduction of nitric oxide with hydrogen in steady-state conditions at 320 K and 390 K in a 30:1 mixture of H₂ and NO (total pressure = 10⁻⁴ mbar). After steady-state NO reduction, molecularly adsorbed NO in both the linear on-top and threefold coordinations, NH_ads and N_ads species were identified by XPS. The coverage of the NH_ads and N_ads species was higher after the reaction at 390 K than the corresponding values at 320 K. Strong destabilisation of N_ads by O_ads was detected. A possible reaction mechanism is discussed.     

具焙烧服役史钛白粉对新制脱硝催化剂活性影响机制研究

市场上废剂回收再生钛白粉以及催化剂生产企业产生的废料逐渐成为两类广泛使用的廉价钛白粉来源以降低成本。为探究两类具有焙烧服役史物料回用制备新催化剂的可能性及其对催化剂性能影响的微观作用机制,本工作将两类料按不同比例混掺制备出新催化剂样品,进行了脱硝活性测试。并结合拉曼光谱（Raman）、NH3程序升温脱附（NH3-TPD）、氢气程序升温还原(H2-TPR)、原位红外（in situ-FTIR）等手段对催化剂进行分析,探究焙烧服役史对催化剂活性的潜在影响。结果表明：具有焙烧服役史钛白粉混掺量过高则成品活性有所下降,性能下降与比表面积变化、酸性位点等均无密切联系,其根本原因是混掺料残存V2O5发生了过烧团聚,由单分散向结晶态转变,氧化还原性得到一定程度损失。在酸性无显著变化前提下,由于氧化还原受影响,从而抑制了其活性。这启示了未来应用具有焙烧服役史物料,除了考虑比表面积影响,还应着重考虑V物种高温服役烧结带来的氧化还原性能损失。     

微波辐射法制备Cu-SSZ-13催化剂及其对柴油车尾气NOx的脱除

采用微波辐射法和传统水热法分别制备了Cu-SSZ-13催化剂,用于柴油车尾气NO_x的脱除.用X射线衍射(XRD)、N₂物理吸脱附、H₂程序升温还原(H₂-TPR)、电子顺磁共振(EPR)、NH₃程序升温脱附(NH₃-TPD)、电感耦合等离子体质谱(ICP-MS)及X射线光电子能谱(XPS)等方法对样品进行表征.结果表明,微波辐射法大大缩短了SSZ-13分子筛的晶化时间,晶化9 h制得样品的结晶度与传统水热法晶化72 h制得样品的结晶度相近,同时孔结构参数也得到了一定程度的改善,微波辐射法制备样品的Brönsted(B)酸性位和Lewis(L)酸性位增多,活性组分铜的负载量也得到显著的提高,使得微波辐射法制备的催化剂呈现出优异的低温活性和水热稳定性.     

Nanoparticle Opportunities:

Major advances in understanding aerosol formation and growth allow now production of nanoparticles with closely controlled characteristics so that some of the early promises of nanotechnology are materialized. The production of flame‐made titania particles coated in‐situ with vanadia was brought from a microreactor (4 g/h) to a pilot‐scale reactor (up to 200 g/h). Corresponding mixtures of titanium‐ and vanadium‐alkoxides were evaporated into a nitrogen or hydrogen stream and fed into a turbulent hydrogen/air or hydrogen/oxygen flame using a commercial burner. By controlling gas flow rates, burner configuration and type of oxidant, particles with a wide range of characteristics were made. Rutile rich (>85 wt%) to pure anatase (>99.5 wt%) powders were made by exchanging air with oxygen. Vanadia/titania catalysts were made with up to 10 wt% V₂O₅ and were compared to powders made in the flame microreactor. A representative flame‐made DeNOx catalyst exhibited twice as much activity as a conventionally prepared reference catalyst for the removal of NO from a model exhaust gas by selective catalytic reduction with ammonia.     

冷等离子体协同催化反应

冷等离子体与催化协同反应是一个新的化学研究方向.本文总结了利用协同反应研究脱硝反应和几类化学反应取得的成果.包括NO分解反应、CH4选择性催化还原反应、NH3选择性催化还原反应、同时脱硝和脱除PM2.5过程、VOCs脱除、CO2分解以及丙烷二氧化碳重整等反应.协同作用使这些反应实现了低温或室温下的高活性.