Ordered mesoporous materials in catalysis

4.4. Pd on Modified Silica 159 4.5. Pd on Clay and Other Inorganic Materials 159 5. Stille, Fukuyama, and Negishi Reactions 159 5.1. Stille Reactions 159 5.1.1. Pd on Carbon (Pd/C) 159 5.1.2. Palladium on KF/Al2O3 159 5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159 5.2. Fukuyama Reactions 159 5.2.1. Pd on Carbon (Pd/C) 159 5.2.2. Pd(OH)2 on Carbon (Perlman’s Catalyst) 160 5.3. Pd/C-Catalyzed Negishi Reactions 160 6. Ullmann-Type Coupling Reactions 161 6.1. Pd/C-Catalyzed Aryl−Aryl Coupling 161 6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20133-173.pdf

Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

The Hydrothermal Synthesis of Zeolites: History and Development from the Earliest Days to the Present Time

A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used has been described as the active catalytic species. However, recent research has begun to shed light on the in situ transformations that many palladium precatalysts undergo during and before the catalytic reaction, and there are now many suggestions in the literature that narrow the scope of types of palladium that may be considered true “catalysts” in these coupling reactions. In this work, for each type of precatalyst, the recent literature is summarized and the type(s) of palladium that are proposed to be truly active are enumerated. All forms of palladium, including discrete soluble palladium complexes, solid-supported metal ligand complexes, supported palladium nano- and macroparticles, soluble palladium nanoparticles, soluble ligand-free palladium, and palladium-exchanged oxides are considered and reviewed here. A considerable focus is placed on solid precatalysts and on evidence for and against catalysis by solid surfaces vs. soluble species when starting with various precatalysts. The review closes with a critical overview of various control experiments or tests that have been used by authors to assess the homogeneity or heterogeneity of catalyst systems.

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review

Conjugated microporous polymers (CMPs) are a class of organic porous polymers that combine π-conjugated skeletons with permanent nanopores, in sharp contrast to other porous materials that are not π-conjugated and with conventional conjugated polymers that are nonporous. As an emerging material platform, CMPs offer a high flexibility for the molecular design of conjugated skeletons and nanopores. Various chemical reactions, building blocks and synthetic methods have been developed and a broad variety of CMPs with different structures and specific properties have been synthesized, driving the rapid growth of the field. CMPs are unique in that they allow the complementary utilization of π-conjugated skeletons and nanopores for functional exploration; they have shown great potential for challenging energy and environmental issues, as exemplified by their excellent performance in gas adsorption, heterogeneous catalysis, light emitting, light harvesting and electrical energy storage. This review describes the molecular design principles of CMPs, advancements in synthetic and structural studies and the frontiers of functional exploration and potential applications.

Conjugated microporous polymers: design, synthesis and application

Incorporation of gallium into zeolites: syntheses, properties and catalytic application.

The influence of the aluminum contents of MCM-41 (Si/Al ratio varied between 2.7 and 69) on the coordination of Al, on the acidity, and on the catalytic properties is studied by 27Al MAS NMR, temperature programmed desorption of ammonia, and the conversion of acetone. Based on TPDA results, an assignment of the peaks of desorption of ammonia is proposed. With low Al contents, the concentration of strong Bronsted acid sites, which are attributed to tetrahedral aluminum, increases with growing Al amounts. At higher Al contents, however, the number of strong acid sites decreases again. Besides usual strong Bronsted sites, TPDA reveals the existence of weak Bronsted and Lewis sites and of Lewis sites of a high acidic strength. Separation between the two types of sites of weak acidity is incomplete. In the temperature programmed decomposition of NH4-exchanged MCM-41 samples, strong Lewis acid sites temporarily re-adsorb ammonia generated by the thermal decomposition of the NH4+ ions located at the Bronsted sites. Ammonia re-adsorption at Lewis sites results in a shift of the maximum of the TPDA peak to a higher temperature. Calcination of samples leads to the formation of strong Lewis sites at the expense of Bronsted sites. To evaluate the acidity of Al-MCM-41, recording of decomposition profiles has been extended to Ga- and Fe-MCM-41. Catalytic activity in the conversion of acetone reaches its maximum with the sample based on Al-MCM-41 with the molar Si/Al ratio of 6.85. Highly favored formation of isobutene points to a comparably high acidic strength of the active sites.

Acidity and active sites of Al-MCM-41

Physico-chemical and catalytic properties of Al-, Ga- and Fe-substituted mesoporous materials related to MCM-41

Incipient wetness impregnation of zeolite Y with copper(II) nitrate solution and inert activation at 650 °C led to active catalysts for the oxidative carbonylation of methanol to dimethyl carbonate in the gas phase. Activities were measured under elevated pressure (0.4–1.6 MPa) with feed compositions of CO/MeOH/O 2  = 40/20/6–1.5 vol.% (balanced by N 2 ) over zeolite Y loaded with 10–17 wt.% copper. It could be shown that inert activation at 650 °C enhanced the activity, and that Cu loading of 14–17 wt.% gave the best performance. By combined XRD, TEM, TPR and DRIFT characterization it was found that the inert activation initiated dispersion of crystalline CuO, auto-reduction of Cu 2+ to Cu + and redistribution of copper ions with enrichment inside the supercages of the zeolite. The O 2 content of the feed was found to control the selectivity to dimethyl carbonate. Dimethyl carbonate selectivities of 70–75% were achieved within the temperature range of 140–170 °C at an O 2 content of 1.5 vol.%. This allowed space-time yields of dimethyl carbonate up to 632 g l cat −1  h −1 at methanol conversions of 5–12%. Formation of the main side product, dimethoxymethane, was surprisingly affected by CO, which is not in line with suggested reaction pathways. A mechanism is proposed including formation of surface carbonate structures as common intermediate.

Oxidative gas phase carbonylation of methanol to dimethyl carbonate over chloride-free Cu-impregnated zeolite Y catalysts at elevated pressure

The NO, NO/O2, and NO/O2/H2O adsorption on MnO2/NaY (5 and 15 wt.% MnO2) composite catalyst and NaY has been studied by means of in situ FTIR and EPR spectroscopy at elevated temperatures and during heating under reaction-like conditions. NO adsorption and co-adsorption of NO and O2 on NaY and MnO2/NaY proceeds via oxidation of NO forming NO2− and NO3− species. Whereas the manganese dioxide preferably acts as oxidising agent, the zeolite stores the NOx species as nitrite and nitrate ions in the solid. In the presence of oxygen, the nitrate formation is enhanced due to additional oxidation of NO through gaseous oxygen leading to NO2. Dimerisation of NO2 to N2O4 and following disproportionation of the latter causes the formation of NO+ and NO3− species which are associated with nucleophilic zeolitic oxygen and especially alkali cations of the zeolite, respectively. The presence of oxygen facilitates reoxidation of Mn2+ which keeps more Mn ions in the active state. Pre-adsorbed water and higher amounts of water vapour in the feed hinder the NO adsorption by blocking the adsorption sites and shift the nitrate formation to higher temperatures. The quantities and thermal stability of the nitrates formed during NO and NO/O2 adsorption differs which points to a different mechanism of nitrate formation. In the absence of gaseous oxygen, nitrates are formed by participation of only lattice oxygen. In the presence of oxygen, nitrate formation by dimerisation and disproportionation reactions of NO2 dominates. The manganese component of the composite catalyst supports the oxidation of NO to nitrite and subsequently to nitrate. During this process Mn4+ is reduced to Mn2+ as evidenced by in situ EPR measurements.

Rolf Fricke

Papers

Incorporation of gallium into zeolites: syntheses, properties and catalytic application.

Acidity and active sites of Al-MCM-41

Physico-chemical and catalytic properties of Al-, Ga- and Fe-substituted mesoporous materials related to MCM-41

Oxidative gas phase carbonylation of methanol to dimethyl carbonate over chloride-free Cu-impregnated zeolite Y catalysts at elevated pressure

NOx adsorption on MnO2/NaY composite: an in situ FTIR and EPR study