Chenze Qi

Sulfated graphene as an efficient solid catalyst for acid-catalyzed liquid reactions

Graphene with its two-dimensional sheet of sp2-hybridized carbon is a hot topic in the fields of materials and chemistry due to its unique features. Herein, we demonstrate that sulfated graphene is an efficient solid catalyst for acid-catalyzed liquid reactions. The sulfated graphene was synthesized from a facile hydrothermal sulfonation of reduced graphene oxide with fuming sulfuric acid at 180 °C. Combined characterizations of XRD, Raman, and AFM techniques show that G-SO3H has a sheet structure (1–4 layers). IR spectroscopy shows that G-SO3H has a SO bond, and the XPS technique confirms the presence of an S element in G-SO3H. Acid–base titration indicates that the acidic concentration of sulfonic groups in the sulfated graphene is 1.2 mmol g−1. TG curves shows that the decomposition temperature (268 °C) of the sulfonic groups on the sulfated graphene is much higher than that of conventional SO3H-functionalized ordered mesoporous carbon (237 °C). Catalytic tests of the esterification of acetic acid with cyclohexanol, the esterification of acetic acid with 1-butanol, the Peckmann reaction of resorcinol with ethyl acetoacetate, and the hydration of propylene oxide show that sulfated graphene is much more active than the conventional solid acid catalysts of Amberlyst 15, OMC-SO3H, SO3H-functionalized ordered mesoporous silica (SBA-15-SO3H), graphene oxide, and reduced graphene oxide, which is attributed to the fact that the sulfated graphene almost has no limitation of mass transfer due to its unique sheet structure. Very importantly, the sulfated graphene has extraordinary recyclability in these reactions, which is attributed to the stable sulfonic groups on the sulfated graphene. The advantages, including high activities and good recyclability as well as simple preparation, are potentially important for industrial applications of the sulfated graphene as an efficient heterogeneous solid acid catalyst in the future.

High-temperature synthesis of strong acidic ionic liquids functionalized, ordered and stable mesoporous polymers with excellent catalytic activities

Strong acidic ionic liquids functionalized, ordered and stable mesoporous phenol–formaldehyde resins (OMR-ILs) monoliths have been successfully synthesized from the treatment of ordered mesoporous resins (OMR-[HMTA]) using 1,3-propanesultone, followed by ion exchanged using various strong acids. The OMR-[HMTA] samples could be synthesized by the assembly of block copolymer template of F127 with preformed resol, which could be obtained from heating a mixture of phenol and formaldehyde at 70 °C; during curing processes, certain contents of the hexamethyltetramine (HMTA) cross linker were also introduced, after hydrothermal treatment at 200 °C for 20 h, calcination at 360 °C under nitrogen, OMR-[HMTA] samples with opened mesopores were obtained. Characterizations suggest that OMR-ILs have ordered and stable mesospores, high BET surface areas, and strong acid strength. Interestingly, OMR-ILs show much higher catalytic activities and recyclability in the esterification of acetic acid with cyclohexanol, hydration of propylene oxide, Peckmann reaction of resorcinol with ethyl acetoacetate and transesterification of tripalmitin with methanol than those of Amberlyst 15, sulfonic group functional ordered mesoporous silicas and acidic zeolites, which were even comparable with that of H2SO4. The unique features of OMR-ILs such as superior thermal stability, excellent catalytic activities and recyclability, will be potentially important for their applications in industry.

Efficient biomass transformations catalyzed by graphene-like nanoporous carbons functionalized with strong acid ionic liquids and sulfonic groups

Strong acid ionic liquids and sulfonic group bifunctional graphene-like nanoporous carbons (GNC-SO3H-ILs) have been synthesized by treating nitrogen containing graphene-like nanoporous carbons (GNCs) with 1,3-propanesultone, ion exchanging with HSO3CF3 or H2SO4. Introducing nitrogen is important for grafting strong acid ionic liquids and sulfonic group in GNCs, which were synthesized from carbonization of a mixture of dicyandiamide or melamine and glucose. GNC-SO3H-ILs possess abundant nanopores, nanosheet structure, good dispersion and controlled acidity. By themselves, they are capable of enhancing the fast diffusion of reactants and products, while increasing the exposure degree of acidic sites in GNC-SO3H-ILs throughout various reactions. The above characteristics resulted in their much improved catalytic activity in biomass transformations such as the production of biodiesel and depolymerization of crystalline cellulose into sugars, which was even comparable to those of homogeneous ionic liquid and mineral acids.

An efficient and recyclable heterogeneous palladium catalyst utilizing naturally abundant pearl shell waste

An efficient and recyclable ligand-free heterogeneous catalyst has been prepared by the immobilization of palladium onto ground pearl shell powders (Pd/shell powders, Pd/SP). The catalytic activity and recyclability of the prepared Pd/SP along with the charcoal and calcium carbonate supported palladium (Pd/C and Pd/CaCO3) catalysts have been evaluated using the reductive homocoupling of aromatic halides. Pd/SP not only has higher catalytic activity, but also exhibits much stronger stability than Pd/C and Pd/CaCO3. The remarkable Pd/SP stability has been attributed to the chelation of palladium species with the surface chitin and protein molecules of the supported pearl shell powders. The X-ray photoelectron spectroscopy (XPS) studies show that the reductive Pd0 species can be regenerated in situ from the oxidative Pd2+ species for the Pd/SP catalyzed reductive homocoupling of aromatic halides in ethanol/DMSO solution, suggesting that the heterogeneous and homogeneous palladium catalysis proceeds through a similar Pd0/Pd2+ cycle catalytic mechanism.

Generalized and high temperature synthesis of a series of crystalline mesoporous metal oxides based nanocomposites with enhanced catalytic activities for benzene combustion

We report here a generalized synthesis of various crystalline mesoporous metal oxides including CeO2, Cr2O3, Fe2O3, SnO2, Ce0.5Zr0.5O2, TiO2, Al2O3 and ZrO2 from the self-assembly of a basic poly 4-vinylpyridine (P4VP) template with various metal precursors based on their strong acid–base interaction under high temperature (180 °C) hydrothermal conditions. Using the typically crystalline mesoporous metal oxide of CeO2, after removing the template by calcination at 550 °C and loading with various transition metal oxides such as MnOx, various transition metal oxide functionalized crystalline mesoporous CeO2 (MnOx/P4VP–CeO2) were obtained. X-ray diffraction (XRD) patterns show that the resulting mesoporous metal oxides exhibit a high degree of crystallinity, and the transition metal oxides active sites have been successfully loaded into these samples. N2 sorption–desorption isotherms, SEM images show that the resulting crystalline mesoporous metal oxides, such as CeO2, have a large BET surface area (94 m2 g−1) and abundant mesopores, which exhibit monolithic morphology with crystal sizes ranging from 5 to 15 μm, giving a uniform pore size centered at 5 nm. XPS spectra show that the active sites such as MnOx exhibit the phases of MnO2 and Mn2O3 in P4VP–CeO2. H2-TPR curves show that MnOx/P4VP–CeO2 exhibits decreased reductive temperatures of both active sites of the MnOx and P4VP–CeO2 supporter when compared with the samples reported previously. More importantly, MnOx/P4VP–CeO2 exhibits much better catalytic activities and good recyclability for catalyzing the oxidation of benzene than that of MnOx loaded commercially crystalline CeO2, which will be very important for their wide applications for VOCs removal in industry.

Superoleophilic nanoporous polymeric ionic liquids loaded with palladium acetate: Reactants enrichment and efficient heterogeneous catalysts for Suzuki–Miyaura coupling reaction

We report here successful synthesis of superoleophilic, nanoporous polymeric ionic liquids supported palladium acetate (PDVB-[C3vim][SO3CF3]-Pd-xs, where x stands for the weight percentage of palladium acetate), which act as efficient heterogeneous catalysts in Suzuki-Miyaura cross-coupling reaction. PDVB-[C3vim][SO3CF3] support was synthesized from solvothermal copolymerization of divinylbenzene with vinylimidazole without using any templates, followed by functionalized with ionic liquid groups. The resultant PDVB-[C3vim][SO3CF3]-Pd-xs possess large BET surface areas, good stability, homogeneous dispersion of Pd active species, and superwettability for various aromatic reactants, which result in their much improved reactants enrichment property. The above characters make PDVB-[C3vim][SO3CF3]-Pd-xs showed much improved catalytic activity and good recyclability in Suzuki-Miyaura reaction in comparison with those of palladium acetate supported onto activated carbon and ordered mesoporous silica of SBA-15. The superior activity found in PDVB-[C3vim][SO3CF3]-Pd-xs is attributed to synergistic effects between large surface areas and unique enrichment property for various aromatic reactants, which by themselves are capable of enhancing exposition degree of Pd active sites to reactants.

Design and synthesis of micro–meso–macroporous polymers with versatile active sites and excellent activities in the production of biofuels and fine chemicals

Micro–meso–macroporous polymers (MOPs) grafted with versatile functional groups, such as sulfonate, amine, triazole, pyridine, strong acidic ionic liquids and triphenylphosphine, were synthesized by in situ cross-linking of different functional molecules with 1,4-bis(chloromethyl)benzene in the presence of Lewis acid catalysts without using additional templates. The resultant hyper-cross-linked nanoporous polymers show unique characteristics such as large BET surface areas (up to 1523 m2 g−1), abundant micro–meso–macropores (4.5–131 nm), and tunable and versatile active sites (acid, base and palladium). These functional polymers exhibit excellent activities and good reusability in biomass conversions, cross-coupling reactions and condensation. The catalytic activities are much better than those of various conventional catalysts such as H3PW12O40, SBA-15-SO3H, Amberlyst 15, and mesoporous H-ZSM-5 Pd/C and even as comparable as those of homogeneous H2SO4 and HCl in the depolymerization of crystalline cellulose into fine chemicals and towards transesterification to biodiesel. This work highlights a low cost route to the synthesis of solid catalysts based on functional nanoporous polymers for catalyzing the production of clean biofuels and fine chemicals.

Ordered Mesoporous Polymers for Biomass Conversions and Cross‐Coupling Reactions

Amino group-functionalized, ordered mesoporous polymers (OMP-NH2 ) were prepared using a solvent-free synthesis by grinding mixtures of solid raw precursors (aminophenol, terephthaldehyde), using block copolymer templates, and curing at 140-180 °C. OMP-NH2 was functionalized with acidic sites and incorporated with palladium, giving multifunctional solid catalysts with large Brunauer-Emmett-Teller (BET) surface areas, abundant and ordered mesopores, good thermal stabilities, controllable concentrations, and good dispersion of active centers. The resultant solid catalysts showed excellent catalytic activities and good reusability in biomass conversions and cross-coupling reactions-much superior to those of various reported solid catalysts such as Amberlyst 15, SBA-15-SO3 H, and Pd/C and comparable to those of homogeneous catalysts such as heteropoly acid, HCl, and palladium acetate. A facile green approach was developed for the synthesis of ordered mesoporous polymeric solid catalysts with excellent activities for conversion of low-cost feedstocks into useful chemicals and clean biofuels.

Template-free synthesis of porous carbonaceous solid acids with controllable acid sites and their excellent activity for catalyzing the synthesis of biofuels and fine chemicals

N rich porous carbon based solid acids (NPC-[CxN][X]) have been successfully synthesized by treatment of N rich porous carbon (NPC) with various quaternary ammoniation reagents such as iodomethane, 1,3-propane sultone, and 1,4-butanesultone, and ion exchange with various strong acids such as HSO3CF3, H2SO4, H3PW12O40, HBF4etc. The NPC support was synthesized by carbonization of KOH-activated polypyrrole without using additional templates. Various characterizations showed that NPC-[CxN][X] possesses abundant nanopores, large Brunauer–Emmett–Teller surface areas, good stability, and strong and controllable acid sites with Bronsted characteristics. The immobilized acidic groups were homogeneously dispersed into NPC-[CxN][X]. Notably, NPC-[CxN][X] acted as efficient, reusable and generalized solid acids, which showed excellent activity in various acid-catalyzed reactions such as esterification and transesterification in the synthesis of biodiesel, dehydration of fructose into 5-hydroxymethylfurfural, depolymerization of crystalline cellulose into sugars, and condensation of phenol with acetone in the synthesis of bisphenol A, much higher than that of various solid acids such as Amberlyst 15, H-ZSM-5, H-USY, and sulfonic group functionalized ordered mesoporous silicas. The preparation of NPC-[CxN][X] leads to the development of porous carbon based solid acids with controllable structural characteristics and excellent catalytic activity.

Study of CeO2 Modified AlNi Mixed Pillared Clays Supported Palladium Catalysts for Benzene Adsorption/Desorption-Catalytic Combustion

A new functional AlNi-pillared clays (AlNi-PILC) with a large surface area and pore volume was synthesized. The performance of adsorption/desorption-catalytic combustion over CeO2-modified Pd/AlNi-PILC catalysts was also studied. The results showed that the d001-value and specific surface area (SBET) of AlNi-PILC reached 2.11 nm and 374.8 m2/g, respectively. The large SBET and the d001-value improved the high capacity for benzene adsorption. Also, the strong interaction between PdCe mixed oxides and AlNi-PILC led to the high dispersion of PdO and CeO2 on the support, which was responsible for the high catalytic performance. Especially, 0.2% Pd/12.5% Ce/AlNi-PILC presented high performance for benzene combustion at 240 °C and high CO2 selectivity. Also, the combustion temperatures were lower compared to the desorption temperatures, which demonstrated that it could accomplish benzene combustion during the desorption process. Furthermore, its activity did not decrease after continuous reaction for 1000 h in dry air, and it also displayed good resistance to water and the chlorinated compound, making it a promising catalytic material for the elimination of volatile organic compounds.