Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.
ABSTRACT: Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.
Project description:Lignin is recognized as a good sustainable material because of its great abundance and potential applications. At present, lignin hydrogenolysis is considered as a potential but challenging way to produce low-molecular-mass aromatic chemicals. The most common linkage between the structural units of lignin polymer is the β-O-4 aryl ether, which are primary or even only target chemical bonds for many degradation processes. Herein, a Pd-Fe₃O₄ composite was synthesized for catalytic hydrogenolysis of β-O-4 bond in lignin. The synthesized catalyst was characterized by XRD, XPS, and SEM and the lignin depolymerization products were analyzed by GC-MS. The catalyst showed good catalytic performance during the hydrogenolysis process, lignin dimer was degraded into monomers completely and a high yield of monomers was obtained by the hydrogenolysis of bagasse lignin. More importantly, the magnetic catalyst was separated conveniently by magnet after reaction and remained highly catalytically efficient after being reused for five times. This work has demonstrated an efficient & recyclable catalyst for the cleavage of the β-O-4 bond in lignin providing an alternative way to make better use of lignins.
Project description:Arenes are widely used chemicals and essential components in liquid fuels, which are currently produced from fossil feedstocks. Here, we proposed the self-supported hydrogenolysis (SSH) of aromatic ethers to produce arenes using the hydrogen source within the reactants, and it was found that RuW alloy nanoparticles were very efficient catalyst for the reactions. This route is very attractive and distinguished from the reported studies on the cleavage of the CAr?O bonds. The unique feature of this methodology is that exogenous hydrogen or other reductant is not required, and hydrogenation of aromatic rings could be avoided completely. The selectivities to arenes could reach >99.9% at complete conversion of the ethers. Moreover, lignin could also be transformed into arenes efficiently over the RuW alloy catalyst. The mechanism studies showed that the neighboring Ru and W species in the RuW alloy nanoparticles worked synergistically to accelerate the SSH reaction.
Project description:The direct conversion of untreated microcrystalline cellulose into C2-C3 alcohols, through a one-pot process promoted by the heterogeneous bimetallic Pd/Fe3O4 catalyst, is presented. The process is selfsustainable without the addition of external molecular hydrogen or acid/basic promoters and is mainly selective toward ethanol. At 240 °C, a complete cellulose conversion was reached after 12 h with an ethanol molar selectivity of 51% among liquid products. The synergistic effect played by water (which aids in the chemical pretreatment means of cellulose through the hydrolysis process) and the Pd/Fe3O4 catalyst (which catalyzes the hydrogenolysis reaction driving the pattern of obtained products) is elucidated.
Project description:We report on the synthesis of an alkane-soluble Zintl cluster, [?4-Ge9(Hyp)3]Rh(COD), that can catalytically hydrogenate cyclic alkenes such as 1,5-cyclooctadiene and cis-cyclooctene. This is the first example of a well-defined Zintl-cluster-based homogeneous catalyst.
Project description:C-lignin is a homo-biopolymer, being made up of caffeyl alcohol exclusively. There is significant interest in developing efficient and selective catalyst for depolymerization of C-lignin, as it represents an ideal feedstock for producing catechol derivatives. Here we report an atomically dispersed Ru catalyst, which can serve as an efficient catalyst for the hydrogenolysis of C-lignin via the cleavage of C-O bonds in benzodioxane linkages, giving catechols in high yields with TONs up to 345. A unique selectivity to propenylcatechol (77%) is obtained, which is otherwise hard to achieve, because this catalyst is capable of hydrogenolysis rather than hydrogenation. This catalyst also demonstrates good reusability in C-lignin depolymerization. Detailed investigations by model compounds concluded that the pathways involving dehydration and/or dehydrogenation reactions are incompatible routes; we deduced that caffeyl alcohol generated via concurrent C-O bonds cleavage of benzodioxane unit may act as an intermediate in the C-lignin hydrogenolysis. Current demonstration validates that atomically dispersed metals can not only catalyze small molecules reactions, but also drive the transformation of abundant and renewable biopolymer.
Project description:A disadvantage of the commercial Raney Ni is that the Ni active sites are prone to leaching and deactivation in the hydrogenation of xylose to xylitol. To explore a more stable and robust catalyst, activated carbon (AC) supported Ni-Re bimetallic catalysts (Ni-Re/AC) were synthesized and used to hydrogenate xylose and hemicellulosic hydrolysate into xylitol under mild reaction conditions. In contrast to the monometallic Ni/AC catalyst, bimetallic Ni-Re/AC exhibited better catalytic performances in the hydrogenation of xylose to xylitol. A high xylitol yield up to 98% was achieved over Ni-Re/AC (nNi:nRe = 1:1) at 140 °C for 1 h. In addition, these bimetallic catalysts also had superior hydrogenation performance in the conversion of the hydrolysate derived from the hydrolysis reaction of the hemicellulose of Camellia oleifera shell. The characterization results showed that the addition of Re led to the formation of Ni-Re alloy and improved the dispersion of Ni active sites. The recycled experimental results revealed that the monometallic Ni and the bimetallic Ni-Re catalysts tended to deactivate, but the introduction of Re was able to remarkably improve the catalyst's stability and reduce the Ni leaching during the hydrogenation reaction.
Project description:Carbon-supported mono- and bimetallic catalysts prepared via incipient wetness impregnation were systematically studied in aqueous-phase reforming (APR) of xylitol aiming at hydrogen production from biomass. The catalytic performance of several VIII group metals and their combinations, such as Pt, Ni, Pt-Ni, Re, Pt-Re, Ru, Pt-Ru, and Pt-Co, was compared for xylitol APR in a fixed-bed reactor at 225 °C and 29.7 bar (N2). Ni/C, Ru/C, and Re/C catalysts displayed significantly lower activity compared to others. Activity and selectivity to H2 of bimetallic Pt-Ni/C, Pt-Co/C, and Pt-Ru/C catalysts were close to that of Pt/C. Pt-Re/C catalyst showed an outstanding performance which was accompanied by a shift of the reaction pathways to the alkane formation and thereby lower hydrogen selectivity. Addition of the second metal to Pt was not found to be beneficial for hydrogen production, thus leaving Pt/C as the optimum carbon-supported catalyst.
Project description:Chemoselective deoxygenation by hydrogen is particularly challenging but crucial for an efficient late-stage modification of functionality-laden fine chemicals, natural products, or pharmaceuticals and the economic upgrading of biomass-derived molecules into fuels and chemicals. We report here on a reusable earth-abundant metal catalyst that permits highly chemoselective deoxygenation using inexpensive hydrogen gas. Primary, secondary, and tertiary alcohols as well as alkyl and aryl ketones and aldehydes can be selectively deoxygenated, even when part of complex natural products, pharmaceuticals, or biomass-derived platform molecules. The catalyst tolerates many functional groups including hydrogenation-sensitive examples. It is efficient, easy to handle, and conveniently synthesized from a specific bimetallic coordination compound and commercially available charcoal. Selective, sustainable, and cost-efficient deoxygenation under industrially viable conditions seems feasible.
Project description:Herein, a lignin-centered convergent approach to produce either aliphatic or aromatic bio-hydrocarbons is introduced. First, poplar or spruce wood was deconstructed by a lignin-first biorefining process, a technique based on the early-stage catalytic conversion of lignin, yielding lignin oils along with cellulosic pulps. Next, the lignin oils were catalytically upgraded in the presence of a phosphidated Ni/SiO2 catalyst under H2 pressure. Notably, selectivity toward aliphatics or aromatics can simply be adjusted by changes in H2 pressure and temperature. The process renders two distinct main cuts of branched hydrocarbons (gasoline: C6-C10, and kerosene/diesel: C14-C20). As the approach is H2-intensive, we examined the utilization of pulp as an H2 source via gasification. For several biomass sources, the H2 obtainable by gasification stoichiometrically meets the H2 demand of the deep converting lignin-first biorefinery, making this concept plausible for the production of high-energy-density drop-in biofuels.
Project description:More efficient use of lignin carbon is necessary for carbon-efficient utilization of lignocellulosic biomass. Conversion of lignin into valuable aromatic compounds requires the cleavage of C-O ether bonds and C-C bonds between lignin monomer units. The catalytic cleavage of C-O bonds is still challenging, and cleavage of C-C bonds is even more difficult. Here, we report cleavage of the aromatic C-O bonds in lignin model compounds using supported metal catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of the aromatic rings. The cleavage of the C-C bond in bibenzyl was also achieved with Rh/C as a catalyst. Use of this technique may greatly facilitate the conversion of lignin into valuable aromatic compounds.