Electronic supplementary material from Cerium promoted V-g-C₃N₄ as highly efficient heterogeneous catalysts for the direct benzene hydroxylation

Cerium promoted V-g-C3N4 as highly efficient heterogeneous catalysts for the direct benzene hydroxylatio

Four organic–inorganic compounds based on polyoxometalates: crystal structures and catalytic epoxidation of styrene

<div><p>Four compounds based on polyoxometalates, [Cu(4-bpo)(H₂O)][Cu₂(<i>μ</i>₂-Cl)(4-bpo)₂(H₂O)][SiW₁₂O₄₀][N(CH₃)₄]₂·H₂O (<b>1</b>), [Cu(4-bpo)]₄[P₂W₁₈O₆₂][N(CH₃)₄]₂·6H₂O (<b>2</b>), [Cu₂(<i>μ</i>₂-OH)(4-bpo)₂(Hina)(H₂O)₂]₂[P₂W₁₈O₆₂]·4H₂O (<b>3</b>), and [Cu₂(Hina)₄(H₂O)₂][H₂P₂W₁₈O₆₂](Hina)·11H₂O (<b>4</b>) (4-bpo=2,5-bis(4-pyridyl)-1,3,4-oxadiazole, ina=isonicotinic acid), have been hydrothermally synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The 3-D framework of <b>1</b> is composed by Keggin-type polyoxoanions {SiW₁₂} and two types of infinite chains, {Cu(4-bpo)(H₂O)}_<i>n</i> and {Cu₂(<i>μ</i>₂-Cl)(4-bpo)₂(H₂O)}_<i>n</i>, through hydrogen bonds. Compound <b>2</b> has a 3-D rigid framework which is fabricated by Wells–Dawson type polyoxoanions {P₂W₁₈} and Cu-(4-bpo) chains through covalent bonds. Compound <b>3</b> contains an infinite {Cu₂(<i>μ</i>₂-OH)(4-bpo)₂(Hina)(H₂O)₂}_<i>n</i> double-chain and {P₂W₁₈} polyoxoanions immobilized in the voids between the chains. Compound <b>4</b> exhibits a 3-D supramolecular network directed by hydrogen bonds between {P₂W₁₈} polyoxoanions and the double paddle-wheel {Cu₂(Hina)₄(H₂O)₂}. Compounds <b>1–4</b> were tested as heterogeneous catalysts for the epoxidation of styrene using <i>tert-</i>butyl hydroperoxide (TBHP) as oxidant. The compounds show catalytic activity with <b>2</b> giving the highest yield of styrene oxide.</p></div

Microexplosion under Microwave Irradiation: A Facile Approach to Create Mesopores in Zeolites

A facile microexplosion approach has been successfully developed to produce an interwoven mesopore network in zeolite crystals via the rushing-out of gases generated by decomposition of H₂O₂ under microwave irradiation. This “gas imprint” method creates the mesopores from the interior crystal toward the exterior, in line with the direction of the pristine microporous channels, and is different from the previous methods in which the reagent starts an attack from the crystal surface and perforates inward. The created mesopores extend throughout the whole crystal and highly blend into the intrinsic micropores around. The acidity of zeolite is also well preserved due to this unique mechanism of pore creation. The continuous high quality hierarchical architecture with intact acidity leads to a notable increase both in the conversion of 2-methoxynaphthalene acylation and in the selectivity to the target molecule of 2-acetyl-6-methoxynapthalene. This microexplosion approach offers an efficient synthesis protocol of zeolitic hierarchy integrating intersected mesoporosity and zeolitic microporosity and opens the way to the rational organization of meso- and microporosity for maximal advantage in applications