Conversion of CO2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst.

A highly efficient homogeneous catalyst system for the production of CH3OH from CO2 using pentaethylenehexamine and Ru-Macho-BH (1) at 125-165 °C in an ethereal solvent has been developed (initial turnover frequency = 70 h(-1) at 145 °C). Ease of separation of CH3OH is demonstrated by simple distillation from the reaction mixture. The robustness of the catalytic system was shown by recycling the catalyst over five runs without significant loss of activity (turnover number > 2000). Various sources of CO2 can be used for this reaction including air, despite its low CO2 concentration (400 ppm). For the first time, we have demonstrated that CO2 captured from air can be directly converted to CH3OH in 79% yield using a homogeneous catalytic system.

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H2) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen.

Catalysts based on suitable metal oxide supports, such as NiO/MgO and CoO/MgO, were shown to be active for single step bi-reforming, the combined steam and dry reforming of methane or natural gas with H2O and CO2 exclusively to metgas (CO-2H2) for efficient methanol synthesis. Reactions were carried out in a tubular flow reactor under pressures up to 42 bar at 830-910 °C. Using a CH4 to steam to CO2 ratio of ∼3:2:1 in the gas feed, the H2/CO ratio of 2:1 was achieved, which is desired for subsequent methanol synthesis. The needed 2/1 steam/CO2 feed ratio together with the reaction heat for the endothermic bi-reforming can be conveniently obtained by the complete combustion of a quarter part of the overall used methane (natural gas) with oxygen of the air (oxidative bi-reforming). Complete combustion of a part of methane followed by bi-reforming leads to the production of metgas (H2/CO in 2:1 mol ratio) for self-sufficient exclusive methanol synthesis. The long sought after but elusive efficient and selective oxygenation of methane to methanol is thus achieved in an effective and economic way without any oxidation byproduct formation according to CH4 + 1/2O2 → CH3OH.

Recycling of carbon dioxide to methanol and derived products - closing the loop.

Starting with coal, followed by petroleum oil and natural gas, the utilization of fossil fuels has allowed the fast and unprecedented development of human society. However, the burning of these resources in ever increasing pace is accompanied by large amounts of anthropogenic CO2 emissions, which are outpacing the natural carbon cycle, causing adverse global environmental changes, the full extent of which is still unclear. Even through fossil fuels are still abundant, they are nevertheless limited and will, in time, be depleted. Chemical recycling of CO2 to renewable fuels and materials, primarily methanol, offers a powerful alternative to tackle both issues, that is, global climate change and fossil fuel depletion. The energy needed for the reduction of CO2 can come from any renewable energy source such as solar and wind. Methanol, the simplest C1 liquid product that can be easily obtained from any carbon source, including biomass and CO2, has been proposed as a key component of such an anthropogenic carbon cycle in the framework of a "Methanol Economy". Methanol itself is an excellent fuel for internal combustion engines, fuel cells, stoves, etc. It's dehydration product, dimethyl ether, is a diesel fuel and liquefied petroleum gas (LPG) substitute. Furthermore, methanol can be transformed to ethylene, propylene and most of the petrochemical products currently obtained from fossil fuels. The conversion of CO2 to methanol is discussed in detail in this review.

Bi-reforming of methane from any source with steam and carbon dioxide exclusively to metgas (CO-2H2) for methanol and hydrocarbon synthesis.

A catalyst based on nickel oxide on magnesium oxide (NiO/MgO) thermally activated under hydrogen is effective for the bi-reforming with steam and CO(2) (combined steam and dry reforming) of methane as well as natural gas in a tubular flow reactor at elevated pressures (5-30 atm) and temperatures (800-950 °C). By adjusting the CO(2)-to-steam ratio in the gas feed, the H(2)/CO ratio in the produced syn-gas could be easily adjusted in a single step to the desired value of 2 for methanol and hydrocarbon synthesis.

Self-sufficient and exclusive oxygenation of methane and its source materials with oxygen to methanol via metgas using oxidative bi-reforming.

A combination of complete methane combustion with oxygen of the air coupled with bi-reforming leads to the production of metgas (H2/CO in 2:1 mole ratio) for exclusive methanol synthesis. The newly developed oxidative bi-reforming allows direct oxygenation of methane to methanol in an overall economic and energetically efficient process, leaving very little, if any, carbon footprint or byproducts.

Carbon dioxide capture from the air using a polyamine based regenerable solid adsorbent.

Easy to prepare solid materials based on fumed silica impregnated with polyethylenimine (PEI) were found to be superior adsorbents for the capture of carbon dioxide directly from air. During the initial hours of the experiments, these adsorbents effectively scrubbed all the CO(2) from the air despite its very low concentration. The effect of moisture on the adsorption characteristics and capacity was studied at room temperature. Regenerative ability was also determined in a short series of adsorption/desorption cycles.

Magneto-responsive organogels prepared through surface-initiated atom transfer radical polymerization on iron nanoparticles.

Iron nanoparticles (Fe(np)) with average diameter 50 nm have been synthesized by addition of NaBH4 to FeCl3 solution then radical initiator, (11-(2-bromo-2-methyl)propionyloxy)undecyltrichlorosilane (1) has been immobilized on to Fe(np). Surface-initiated atom transfer radical polymerization (SI-ATRP) of different monomers such as styrene, methyl methacrylate, methacrylonitrile and N-vinylimidazol have been carried out from initiator-grafted Fe(np) and the amount of grafted polymers was determined by thermogravimetric analysis (TGA). Immobilization of PMMA has been monitored by TGA of samples taken from the reaction mixture after 4, 9 and 21 hours. Activators regenerated by electron transfer (ARGET) ATRP of methyl methacrylate and styrene were conducted from initiator-grafted Fe(np) in the presence of phenol and Na-phenoxide respectively and the yields of immobilized polymers were found lower than those we observed in the case of conventional ATRP. The concentration of Fe(np) (c(m)) in the reaction mixture was found to influence significantly the appearance of products; at higher c(m) values SI-ATRP of styrene resulted in the formation of magneto-responsive gels. Transmission electron microscope investigation of bare Fe(np) and magnetic gel revealed that the particles are well-dispersed in the gel while non-grafted Fe(np) form aggregates. XRD measurements were used to determine the composition of magnetic nanoparticles. It was found that the crystalline phase of Fe(np) is mostly reduced iron and the fraction of iron-oxide (hydroxide) species is below the detection limit of XRD. Immobilized polymers have been degrafted by digestion of Fe(np) in HCl and trifluoroacetic acid and the residual polymeric material were identified by FTIR and 1H-NMR spectroscopy. A plausible mechanism for the formation of magnetic gel was given in which polymer network is built up through interparticle termination reactions and Fe(np) act as functional cross-linkers.

A novel approach to magneto-responsive polymeric gels assisted by iron nanoparticles as nano cross-linkers.

A new route for the preparation of magneto-responsive polymeric gels involving iron nanoparticles as nano cross-linkers has been described.

Facile synthesis of high-density poly(octadecyl acrylate)-grafted silica for reversed-phase high-performance liquid chromatography by surface-initiated atom transfer radical polymerization.

To introduce high-density polymeric organic phase onto silica, initiator-modified silica was prepared and then surface-initiated atom transfer radical polymerization (ATRP) ("grafting-from" method) was carried out with octadecyl acrylate. The resultant polymer-grafted silica was characterized by diffuse reflectance infrared Fourier transform, suspension-state (1)H NMR, solid-state (13)C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS-NMR), solid-state (29)Si-CP-MAS-NMR spectroscopies, elemental analysis and differential scanning calorimetry measurements. ATRP-based poly(octadecyl acrylate)-grafted silica (Sil-ODA(n)-1), was used as a stationary phase in high-performance liquid chromatography (HPLC) and the chromatographic behavior was evaluated by the retention studies of polycyclic aromatic hydrocarbons (PAHs) and aromatic positional isomers. Compared with previous poly(octadecyl acrylate)-grafted silica (Sil-ODA(n)), which was prepared by the "grafting-to" method, we have observed longer retention and greater selectivity for Sil-ODA(n)-1 towards PAHs event at higher temperature.

Amine-free reversible hydrogen storage in formate salts catalyzed by ruthenium pincer complex without pH control or solvent change.

Due to the intermittent nature of most renewable energy sources, such as solar and wind, energy storage is increasingly required. Since electricity is difficult to store, hydrogen obtained by electrochemical water splitting has been proposed as an energy carrier. However, the handling and transportation of hydrogen in large quantities is in itself a challenge. We therefore present here a method for hydrogen storage based on a CO2 (HCO3 (-) )/H2 and formate equilibrium. This amine-free and efficient reversible system (>90 % yield in both directions) is catalyzed by well-defined and commercially available Ru pincer complexes. The formate dehydrogenation was triggered by simple pressure swing without requiring external pH control or the change of either the solvent or the catalyst. Up to six hydrogenation-dehydrogenation cycles were performed and the catalyst performance remained steady with high selectivity (CO free H2 /CO2 mixture was produced).

Facile copper-mediated activation of the N-H bond and the oxidative cleavage of the C2-C3 bond in 1H-2-phenyl-3-hydroxy-4-oxoquinoline.

The reaction of 1H-2-phenyl-3-hydroxy-4-oxoquinoline (PhquinH(2); 1) with metallic copper leads to Cu(II)(PhquinH)(2) while in the presence of PPh(3) to Cu(I)(2)Cu(II)(Phquin)(2)(PPh(3))(4). In the presence of tmeda and O(2) ring cleavage occurs to give Cu(II)(tmeda)(PhquinH)(N-baa). Both reactions represent a mild N-H activation and an oxidative C-C bond scission.

Easily regenerable solid adsorbents based on polyamines for carbon dioxide capture from the air.

Adsorbents prepared easily by impregnation of fumed silica with polyethylenimine (PEI) are promising candidates for the capture of CO2 directly from the air. These inexpensive adsorbents have high CO2 adsorption capacity at ambient temperature and can be regenerated in repeated cycles under mild conditions. Despite the very low CO2 concentration, they are able to scrub efficiently all CO2 out of the air in the initial hours of the experiments. The influence of parameters such as PEI loading, adsorption and desorption temperature, particle size, and PEI molecular weight on the adsorption behavior were investigated. The mild regeneration temperatures required could allow the use of waste heat available in many industrial processes as well as solar heat. CO2 adsorption from the air has a number of applications. Removal of CO2 from a closed environment, such as a submarine or space vehicles, is essential for life support. The supply of CO2-free air is also critical for alkaline fuel cells and batteries. Direct air capture of CO2 could also help mitigate the rising concerns about atmospheric CO2 concentration and associated climatic changes, while, at the same time, provide the first step for an anthropogenic carbon cycle.

Hydrogen generation from formic acid decomposition by ruthenium carbonyl complexes. Tetraruthenium dodecacarbonyl tetrahydride as an active intermediate.

The present Minireview covers the formation and the structural characterization of noble metal carbonyl and hydrido carbonyl complexes, with particular emphasis on ruthenium complexes using formic acid as a carbonyl and hydride source. The catalytic activity of these organometallic compounds for the decarboxylation of formic acid, a potential hydrogen storage material, is also reviewed. In addition, the first preparation of [Ru(4)(CO)(12)H(4)] from RuCl(3) and formic acid as well as the catalytic activity of [Ru(4)(CO)(12)H(4)] for the decomposition of formic acid to hydrogen and carbon dioxide are presented.

Synthesis, self-assembling properties, and atom transfer radical polymerization of an alkylated L-phenylalanine-derived monomeric organogel from silica: a new approach to prepare packing materials for high-performance liquid chromatography.

The monomer N'-octadecyl-N(alpha)-(4-vinyl)-benzoyl-L-phenylalanineamide (4) based on L-phenylalanine has been simply but effectively synthesized, and its self-assembling properties have been investigated. FTIR and a variable-temperature (1)H NMR spectroscopic investigation demonstrated that the aggregation of compound 4 in various organic solvents is due to the formation of intermolecular hydrogen bonds among the amide moieties. UV/Vis measurements indicated that the multiple pi-pi interactions of the phenyl groups also contribute to the self-assembly. As was observed by (13)C cross-polarization magic-angle spinning (CP/MAS) NMR and variable-temperature (1)H NMR measurements, the ordered alkyl chains also played an important role in the molecular aggregation by van der Waals interactions. Compound 4 was polymerized by surface-initiated atom transfer radical polymerization from porous silica gel to prepare a packing material for HPLC. The results of thermogravimetric analysis showed that a relatively large amount of polymer was grafted onto the silica surface. The organic phase on silica was in a noncrystalline solid form in which the long alkyl chain exists in a less-ordered gauche conformation. Analysis of chromatographic performance for polyaromatic hydrocarbon samples showed higher selectivity than conventional reversed-phase HPLC packing materials.

Synthesis and characterization of molybdenum oxo complexes of two tripodal ligands: reactivity studies of a functional model for molybdenum oxotransferases.

Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine (L-OH) with MoO2Cl2 in methanol in the presence of NaOMe and PF6- results in the formation of [MoO2(L-O)]PF6. Similarly, the reaction of N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine (L-SH) with MoO2(acac)2 leads to the formation of [MoO2(L-S)]+. The dioxo-molybdenum complex [MoO2(L-O)]+ reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex, tentatively identified as [Mo(IV)O(L-O)(OCH3)]. The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate, thereby mimicking the activity of DMSO reductase and nitrate reductase. Reaction of [MoO2(L-O)]PF6 with PPh3 in other solvents than methanol leads to the formation of the Mo(V) dimer [(L-O)OMo(micro-O)MoO(L-O)](PF6)2. The crystal structures of [MoO2(L-O)]PF6 and the micro-oxo bridged dimer are presented.