A Facile and Scalable Route to the Preparation of Catalytic Membranes with in Situ Synthesized Supramolecular Dendrimer Particle Hosts for Pt(0) Nanoparticles Using a Low-Generation PAMAM Dendrimer (G1-NH2) as Precursor.

Since the first reports of Cu dendrimer-encapsulated nanoparticles (DENs) published in 1998, the dendrimer-templating method has become the best and most versatile method for preparing ultrafine metallic and bimetallic nanoparticles (1-3 nm) with well-defined compositions, high catalytic activity, and tunable selectivity. However, DENs have remained for the most part model systems with limited prospects for scale up and integration into high-performance and reusable catalytic modules and systems for industrial-scale applications. Here, we describe a facile and scalable route to the preparation of catalytic polyvinylidene fluoride (PVDF) membranes with in situ synthesized supramolecular dendrimer particles (SDPs) that can serve as hosts and containers for Pt(0) nanoparticles (2-3 nm). These new catalytic membranes were prepared using a reactive encapsulation process similar to that utilized to prepare Pt DENs by addition of a reducing agent (sodium borohydride) to aqueous complexes of Pt(II) + G4-OH/G6-OH polyamidoamine (PAMAM) dendrimers. However, the SDPs (2.4 µm average diameter) of our new mixed matrix PVDF-PAMAM membranes were synthesized in the dope dispersion without purification prior to film casting using (i) a low-generation PAMAM dendrimer (G1-NH2) as particle precursor and (ii) epichlorohydrin, an inexpensive functional reagent, as cross-linker. In addition, the membrane PAMAM particles contain secondary amine groups (∼1.9 mequiv per gram of dry membrane), which are more basic and thus have higher Pt binding affinity than the tertiary amine groups of the G4-OH and G6-OH PAMAM dendrimers. Proof-of-concept experiments show that our new PVDF-PAMAM-G1-Pt/membranes can serve as highly active and reusable catalysts for the hydrogenation of alkenes and alkynes to the corresponding alkanes using (i) H2 at room temperature and a pressure of 1 bar and (ii) low catalyst loadings of ∼1.4-1.6 mg of Pt. Using cyclohexene as model substrate, we observed near quantitative conversion to cyclohexane (∼98%). The regeneration studies showed that our new Pt/membrane catalysts are stable and can be reused for five consecutive reaction cycles for a total duration of 120 h including 60 h of heating at 100 °C under vacuum for substrate, product, and solvent removal with no detectable loss of cyclohexene hydrogenation activity. The overall results of our study point to a promising, versatile, and scalable path for the integration of catalytic membranes with in situ synthesized SDP hosts for Pt(0) nanoparticles into high-throughput modules and systems for heterogeneous catalytic hydrogenations, an important class of reactions that are widely utilized in industry to produce pharmaceuticals, agrochemicals, and specialty chemicals.

Energy Efficient Synthesis of Ordered Mesoporous Carbon Nitrides with a High Nitrogen Content and Enhanced CO2 Capture Capacity.

Highly ordered mesoporous carbon nitrides (MCN) with 3D structure and a high nitrogen content are successfully prepared for the first time using "uncalcined" mesoporous silica template, KIT-6 and 3-amino-1,2,4-triazole as a single molecular carbon and nitrogen precursor. The prepared MCN with C and N stoichiometry of C3 N5 shows unique CN framework and exhibits the CO2 capture capacity of 5.63 mmol g-1 at 273 K and 30 bar, which is higher than that of MCN with 2D structure and C3 N4 stoichiometry.

Highly Ordered Nitrogen-Rich Mesoporous Carbon Nitrides and Their Superior Performance for Sensing and Photocatalytic Hydrogen Generation.

Mesoporous carbon nitrides (MCN) are fascinating materials with unique semiconducting and basic properties that are useful in many applications including photocatalysis and sensing. Most syntheses of MCN focus on creating theoretically predicted C3 N4 stoichiometry with a band gap of 2.7 eV using a nano-hard templating approach with triazine-based precursors. However, the performance of the MCN in semiconducting applications is limited to the MCN framework with a small band gap, which would be linked with the addition of more N in the CN framework, but this remains a huge challenge. Here, we report a precursor with high nitrogen content, 3-amino-1,2,4-triazole, that enables the formation of new and well-ordered 3D MCN with C3 N5 stoichiometry (MCN-8), which has not been predicted so far, and a low-band-gap energy (2.2 eV). This novel class of material without addition of any dopants shows not only a superior photocatalytic water-splitting performance with a total of 801 µmol of H2 under visible-light irradiation for 3 h but also excellent sensing properties for toxic acids.

Effect of Heat Treatment on the Nitrogen Content and Its Role on the Carbon Dioxide Adsorption Capacity of Highly Ordered Mesoporous Carbon Nitride.

Mesoporous carbon nitrides (MCNs) with rod-shaped morphology and tunable nitrogen contents have been synthesized through a calcination-free method by using ethanol-washed mesoporous SBA-15 as templates at different carbonization temperatures. Carbon tetrachloride and ethylenediamine were used as the sources of carbon and nitrogen, respectively. The resulting MCN materials were characterized with low- and high-angle powder XRD, nitrogen adsorption, high-resolution (HR) SEM, HR-TEM, elemental analysis, X-ray photoelectron spectroscopy, and X-ray absorption near-edge structure techniques. The carbonization temperature plays a critical role in controlling not only the crystallinity, but also the nitrogen content and textural parameters of the samples, including specific surface area and specific pore volume. The nitrogen content of MCN decreases with a concomitant increase in specific surface area and specific pore volume, as well as the crystallinity of the samples, as the carbonization temperature is increased. The results also reveal that the structural order of the materials is retained, even after heat treatment at temperatures up to 900 °C with a significant reduction of the nitrogen content, but the structure is partially damaged at 1000 °C. The carbon dioxide adsorption capacity of these materials is not only dependent on the textural parameters, but also on the nitrogen content. The MCN prepared at 900 °C, which has an optimum BET surface area and nitrogen content, registers a carbon dioxide adsorption capacity of 20.1 mmol g-1 at 273 K and 30 bar, which is much higher than that of mesoporous silica, MCN-1, activated carbon, and multiwalled carbon nanotubes.

Synthesis of nitrogen-rich mesoporous carbon nitride with tunable pores, band gaps and nitrogen content from a single aminoguanidine precursor.

Highly ordered mesoporous carbon nitride (CN) with an extremely high nitrogen content and tunable pore diameters was synthesized by using a new precursor with a high nitrogen content, aminoguanidine hydrochloride and mesoporous silica SBA-15 with different pore diameters as hard templates. Surprisingly, the N/C ratio of the prepared mesoporous CN (MCN-4: 1.80) was considerably higher than that of the theoretically predicted C(3)N(4) nanostructures (1.33). This is mainly due to the fact that the CN precursor easily undergoes polymerization at high temperature and affords a highly stable polymer composed of a diamino-s-tetrazine moiety with a six-membered aromatic ring containing six nitrogen atoms that are linked trigonally with the nitrogen atoms. The obtained materials were thoroughly characterized by means of XRD, nitrogen adsorption, high resolution TEM, electron energy loss spectra, high resolution SEM, X-ray photoelectron spectroscopy, FTIR, and C, N, O, and S analysis. The results show that the MCN-4 materials possess a well-ordered mesoporous structure similar to SBA-15 with a high specific surface area and tunable band gap in the range of 2.25-2.49 eV. Interestingly, the pore diameter of the materials can be finely tuned from 3.1-5.8 nm by increasing the pore diameter of the hard-template SBA-15. The reaction temperature plays a critical role for the formation of MCN, and we found that 400 °C is the best condition to obtain MCN-4 with a high nitrogen content. We have further investigated the catalytic application of the MCN-4 materials towards Friedel-Crafts hexanoylation of benzene and compared the results with the mesoporous CN with less nitrogen content (MCN-1) and nonporous CN. Among the materials studied, MCN-4 showed the highest activity, affording a high yield of hexanophenone within a few hours, which is mainly due to the presence of free amine groups on the wall structure of MCN-4.