Catalysts Based on Porous Polyaromatic Frameworks for Deep Oxidative Desulfurization of Model Fuel in Biphasic Conditions

Abstract

The first example of an application of porous aromatic frameworks (PAFs) in synthesis of catalysts for oxidative desulfurization was described. The mesoporous aromatic framework with a diamondlike structure was modified with tungsten and molybdenum carbonyls, and synthesized catalysts were successfully used for low-temperature oxidation of organic sulfides. The obtained materials were characterized by low-temperature nitrogen adsorption/desorption, transmission electron microscopy, atomic emission spectroscopy, and X-ray photoelectron spectroscopy techniques. It was shown that the polymer did not undergo oxidation and retained its structure in the presence of hydrogen peroxide and tert-butyl hydroperoxide. The catalysts possessed high activity because of the hydrophobic nature of the carrier and their high surface area.

Metal-Free Oxidative Desulfurization Catalysts Based on Porous Aromatic Frameworks

“…The PAF, PAF-30, was synthesized via the Suzuki cross-coupling reaction between tetrakis-(pbromophenyl)methane and 4,4′-biphenyldiboronic acid according to the method described earlier. 18,21,22 Sulfonation of PAF-30 was performed using a solution of chlorosulfonic acid in dichloromethane. PAF-30 (500 mg) was suspended in dichloromethane (25 mL), and the suspension was cooled to 0 °C.…”

“…The PAF, PAF-30, was synthesized via the Suzuki cross-coupling reaction between tetrakis-( p -bromophenyl)­methane and 4,4′-biphenyldiboronic acid according to the method described earlier. ,, …”

“…One kind of mesoporous material, porous aromatic frameworks (PAFs), is of particular interest for the design of catalysts for ODS; their carbonic nature gives them a high affinity for organic compounds, including sulfur compounds, and due to the robust porous structure build of covalently linked aromatic building blocks, they possess high chemical and thermal stability. Recently, PAFs were used to create very active ODS catalysts based on molybdenum 18 and molybdenum-containing polyoxometalates. 13,19 Salts or oxides of transition metals such as molybdenum, tungsten, and vanadium are most often used as the active phase because they can form a peroxocomplex in the presence of hydrogen peroxide.…”

Catalysts Based on Acidic SBA-15 for Deep Oxidative Desulfurization of Model Fuels

“…Transition-metal oxides are the most widely used catalysts for oxidative desulfurization. − Such catalysts are obtained by applying metal salt to the support, followed by calcination. , In this case, zeolites, mesoporous materials, and polymer matrices are used as supports. − However, because of the pore size from 2 to 50 nm, supports based on SBA-15 are becoming more widespread. , Currently, there are known catalytic systems based on SBA-15 containing oxides of tungsten, molybdenum, and vanadium as catalysts for the oxidation of DBT . However, in the presence of such catalysts, oxidation takes quite a long time (on average, 2 h).…”

Zeolite Stabilized Isolated Molybdenum Species for Catalytic Oxidative Desulfurization

“…据报道, 高空间位阻的硫化物如 二苯并噻吩更容易通过 ODS 去除 [12][13][14][15][16] . 氧化脱硫反应 中使用的催化剂种类繁多, 比如杂多酸体系 [16] 、金属有 机体系 [17][18] 以及负载型催化剂等 [19][20] , 其中负载型氧化 钼催化剂表现出优异的催化性能 [13,[21][22][23][24] .…”