Biomass-derived Aldehydes Research Articles

Micellar Transfer Hydrogenation Catalysis in Water with Monocarbonyl Ruthenium(II)-poly(vinylphosphonate)-Containing Polymers: Achieving Reduction of Biomass-Derived Aldehydes

Micellar Transfer Hydrogenation Catalysis in Water with Monocarbonyl Ruthenium(II)-poly(vinylphosphonate)-Containing Polymers: Achieving Reduction of Biomass-Derived Aldehydes

Recent advances on the electrocatalytic oxidation of biomass-derived aldehydes

The escalating demand for sustainable and environmentally benign chemical processes has driven the exploration of biomass as an alternative to non-renewable resources. Electrocatalytic upgrading of biomass-derived aldehydes plays a crucial role in biomass refining, and has become a frontier of mainstream research. This paper reviews the recent advances on the electrocatalytic oxidation of typical biomass-derived aldehydes (5-hydroxymethylfurfural, furfural, glucose, xylose, vanillin and benzaldehyde, etc.). The research presented in this review covers a wide range of oxidation mechanisms for each aldehyde. It is evident from the current literature that challenges related to the comprehensiveness of mechanistic studies, catalyst stability, and reaction scalability remain, but the rapid progress offers hope for future advancements. Finally, we elucidate the challenges in this domain and provide the perspectives on future developments. This review corroborates the significance of investigating the electrocatalytic oxidation of biomass-derived aldehydes and emphasizes the need for continued research to refine these processes for industrial applications.

Rotating Disk Electrode Studies of Benzaldehyde Oxidation on Group Ib Metals

Water electrolysis is a green means of producing hydrogen gas to be used as a fuel or reactant in key industrial processes such as ammonia production. The conventional system of oxygen evolution (OER) and hydrogen evolution (HER) suffers from slow kinetics at the anode and a high cell voltage limited by thermodynamics. One solution is to replace OER with another reaction such as an organic oxidation reaction that has a lower equilibrium potential and produces a valuable organic byproduct at the anode. Recent work has demonstrated that biomass-derived aldehydes such as furfural and 5-hydroxymethylfurfural can be selectively oxidized to their corresponding carboxylates and H2 on Cu-based anodes at low potentials (~0.1 VRHE) in alkaline media. In alkaline media, a hydroxide ion adds to the carbonyl carbon of an aldehyde molecule forming a gem diolate in solution phase. It is argued that dehydrogenation becomes more facile due to the weaker C-H bond of the gem diolate compared to the aldehyde form of the molecule. This may enable oxidation without the need for coadsorbed-OH. Additionally, aldehyde oxidation is only active on Au, Ag, and Cu electrodes at higher pHs.The aim of this work is to identify the conditions under which low potential oxidation of aldehydes and high anodic Faradaic efficiency to H2 occurs, namely, electrode material and applied potential. To avoid polymerization side reactions of furans in alkaline media, we studied benzaldehyde as a model compound which has also been shown to exhibit low potential oxidation and anodic H2. The activity (rate of aldehyde consumption) and selectivity (to anodic H2 versus H2O) were compared for the group Ib metals (Au, Ag, Cu), each of which demonstrates a relatively early onset potential (<0.4 VRHE) and generates anodic H2 at certain potentials. Rotating disk electrode studies with Koutecky-Levich analysis were conducted to separate mass transfer effects from kinetic current to compare the intrinsic activity of each electrode. Additionally, the average number electrons transferred per aldehyde molecule consumed was estimated from Koutecky-Levich analysis; the one-electron pathway combines the aldehyde hydrogens to H2 while the two-electron pathway requires an additional electron per aldehyde molecule to oxidize the hydrogen from the surface to form H2O. Rotating ring disk electrode studies were used to further validate the anodic H2 generation as a Pt ring was still able to oxidize H2 despite the presence of benzaldehyde. This was used as an additional means of estimating the selectivity to H2 as a function of potential.CVs for benzaldehyde oxidation on each metal are shown in Figure a. Peak current followed the order of Au > Ag >> Cu. Au reached a mass transfer limiting current, and Ag also showed an RPM dependence but did not reach full mass transfer limitations. Cu was the least active and did not show any mass transfer dependence. On the other hand, Cu has the earliest onset potential followed by Ag then Au. The average number of electrons transferred per aldehyde molecule according to RRDE measurements is shown in Figure b, where one electron represents H2 and two electrons represents H-oxidation to H2O. Cu had 100% selectivity to H2 over its entire potential window of activity (up to 0.45 VRHE). Au and Ag have high selectivity to H2 at low potentials but decreases to near zero H2 production in the range of 0.6-0.8 VRHE; the decrease in selectivity to H2 on Ag occurs slightly earlier than Au (~0.1 V). H2 selectivity is related to the inability of each metal to oxidize H to H2O at low potentials. Figure 1

Green Synthesis of Nitriles from Biomass-Derived Aldehydes by Evoking Intrinsic Cooperative Effects of Ionic Liquids

Green Synthesis of Nitriles from Biomass-Derived Aldehydes by Evoking Intrinsic Cooperative Effects of Ionic Liquids

Laccase-Mediated Oxygen Reduction in Liquid Flow Fuel Cells for Efficient Oxidation of Biomass-Derived Aldehydes with Co-Generation of Electricity

Laccase-Mediated Oxygen Reduction in Liquid Flow Fuel Cells for Efficient Oxidation of Biomass-Derived Aldehydes with Co-Generation of Electricity

One-pot two-stage biocatalytic upgrading of biomass-derived aldehydes to optically active β-amino alcohols via sequential hydroxymethylation and asymmetric reduction amination

One-pot two-stage biocatalytic upgrading of biomass-derived aldehydes to optically active β-amino alcohols via sequential hydroxymethylation and asymmetric reduction amination.

Highly efficient and stable Ni-based catalyst for selective conversion of biomass-derived aldehydes and ketones to primary amines

Here We report a yolk-shell structured Zr-assisted Ni-based catalyst, which could catalyze the reductive amination of a variety of biomass-derived aldehydes and ketones with high activity and robust stability. The novel LDH-derived Zr assisted-NiAl catalyst exhibits superior stability (>200 h) than traditional supported Ni/Al2O3 catalyst (<75 h) due to strong interaction between Ni0 yolk and NiAl2O4 shell. Outstanding yield of fufurylamine at 99 % is achieved under mild conditions at low temperature of 70 °C with 1 MPa H2. Other aldehydes and ketones are also transformed into primary amines with high yield above 90 % generally under mild conditions. Our study reveals that strong acidity favors the activation of imines, while strengthened hydrogen activation capability of catalyst promotes the dissociation of intermediate secondary amine to primary amine. The appropriate hydrogen activation capability regulated by Zr introduction into LDH-derived NiAl catalyst avoids over-hydrogenation of furyl-, hydroxyl- and imide-groups, which accounts for the high selectivity of mono-primary amine. Importantly, the dependence of mono-primary amine production on appropriate hydrogen activation capability of catalyst proved by this work provides ideas for tailored catalysts in the production of renewable primary amines from biomass.

Direct Synthesis of N-formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO2 Fixation in a Metal-Organic Framework.

Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal-organic framework supported ruthenium catalyst, Ru/MFM-300(Cr). Highly selective production of N-formamides has been observed for a wide range of carbonyl compounds. Synchrotron X-ray powder diffraction reveals the presence of strong host-guest binding interactions via hydrogen bonding and parallel-displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.

Selective photosynthesis of imines from biomass-derived aldehydes over Ni/TiO2

Selective photosynthesis of imines from biomass-derived aldehydes over Ni/TiO2

Electrochemical Aldehyde Oxidation at Gold Electrodes: gem-Diol, non-Hydrated Aldehyde, and Diolate as Electroactive Species.

To date the electroactive species of selective aldehyde oxidation to carboxylates at gold electrodes is usually assumed to be the diolate. It forms with high concentration only in very alkaline electrolytes, when OH- binds to the carbonyl carbon atom. Accordingly, the electrochemical upgrading of biomass-derived aldehydes to carboxylates is believed to be limited to very alkaline electrolytes at many electrode materials. However, OH- -induced aldehyde decomposition in these electrolytes prevents application of electrochemical aldehyde oxidation for the sustainable upgrading of biomass to value-added chemicals at industrial scale. Here, we demonstrate the successful oxidation of aliphatic aldehydes at a rotating gold electrode at pH 12, where only 1 % of the aldehyde resides as the diolate species. This concentration is too small to account for the observed current, which shows that also other aldehyde species (i. e., the geminal diol and the non-hydrated aldehyde) are electroactive. This insight allows developing strategies to omit aldehyde decomposition while achieving high current densities for the selective aldehyde oxidation, making its future industrial application viable.

Aldol condensation of biomass-derived aldehydes and ketones followed by hydrogenation over Ni/HZSM-5 to produce aviation fuel: Role of acid sites

As the aviation sector grows and fossil fuels are utilized, the environment and economy depend on biomass-based aviation fuel. This study investigated acid sites in aldol condensation to produce aviation fuel from biomass-derived aldehydes and ketones over the bifunctional catalyst Ni/HZSM-5. Due to its excellent 10-member ring channels structure, HZSM-5 yielded 63.81% of the targeted condensates as aviation fuel precursor. At 200 °C for 9 h, aldehydes and ketones were converted to 90.32% and 69.53% of the required condensates. Sodium ion-exchange HZSM-5 with different Brönsted acid site quantities was tested for condensation. Brönsted acid sites were the active center for aldol condensation of aldehydes and ketones, increasing product yield. In γ-Al2O3, the overall amount of Brönsted acid and Lewis acid was equivalent to that of HZSM-5, the amount of Lewis acid was much more. The yield of the targeted condensates over γ-Al2O3 was only 46.11%, much lower than that of HZSM-5 (69.53%). Thus, Brönsted acid sites were better than Lewis acid sites for aldol condensation of aldehydes and ketones. The balance of active sites for aldol condensation and hydrogenation increased the intended alkane yield to 62.91% with 20 wt% Ni loading. This study involves improving biomass-based aviation fuel generation.

Efficient electrooxidation of biomass-derived aldehydes over ultrathin NiV-layered double hydroxides films

Efficient electrooxidation of biomass-derived aldehydes over ultrathin NiV-layered double hydroxides films

Natural attapulgite supported nano-Ni catalysts for the efficient reductive amination of biomass-derived aldehydes and ketones

The efficient synthesis of useful primary amines via reductive amination of biomass-based aldehydes and ketones over earth-abundant base metal catalysts is an attractive biomass value-adding technology yet facing lots of challenges. Herein, natural attapulgite (ATP) was applied as support for the fabrication of active Ni catalysts with different Ni loadings (5–30 ​wt%) by the deposition-precipitation method. The Ni/ATP-550 catalyst with 10–15 ​wt% Ni loadings was found to present the highest catalytic performance for the synthesis of valuable 5-amino-1-pentanol (5-AP) via reductive amination of biofurfural-derived 2-hydroxytetrahydropyran among a variety of commonly used oxide supports loaded Ni catalysts, as well as ATP supported nickel catalysts with other loadings, achieving 5-AP yield up to 94%. The intrinsic activity of the Ni/ATP catalysts was found to depend strongly on the Ni0 crystallite size and Ni0 fraction of the catalysts, which generally increased with increasing Ni0 crystallite size and fraction, owing probably to the hydrogenation of imine intermediate is a structure-sensitive reaction. The efficient 10Ni/ATP-550 catalyst also exhibited good activity and stability in the reductive amination of several other biomass-derived aldehydes and ketones to their corresponding primary amines with good to excellent yields (81%–99%). This work provided a clean and efficient natural ATP-supported non-noble metal nickel-based catalytic system for the reductive amination of aldehydes and ketones to synthesize high-value-added primary amines, which could be a promising candidate for the industrial production of amines.

A novel synergistic covalence and complexation bridging strategy based on multi-functional biomass-derived aldehydes and Al(III) for engineering high-quality eco-leather

To get rid of the chrome pollution faced by the leather industry, we explored a novel engineering high-quality eco-leather technology based on the synergistic interactions between biomass-based aldehydes and Al(III). Firstly, dialdehyde xanthan gum (DXG) was prepared to covalently crosslink with the collagen fibers (CFs) via Schiff-base linkages under alkaline conditions, endowing the leather with a shrinkage temperature (Ts) of 80 °C and opening channels for the subsequent penetration of Al species (AL). Secondly, and for this latter purpose, the DXG-tanned leather was acidified to release part of the DXG from the leather according to the dynamic nature of the Schiff-base. Containing suitable oxygen-containing groups (OGs) with excellent complexation capabilities, the released DXG served as masking agents for AL, facilitating the penetration of AL into the inner CFs network for further complexation crosslinking. Consequently, a denser crosslinking network was constructed in the leather, and the crust leather exhibited higher Ts (82.2 °C), improved mechanical (tensile strength: 13.4 N/mm2, tear strength: 53.3 N/mm) and organoleptic properties than those of the DXG crust or AL crust leathers. This demonstrates that this synergistic covalence and complexation bridging strategy is a sustainable option to substitute highly restricted chrome tanning agent for eco-leather production.

Electrochemical conversion of biomass-derived aldehydes into fine chemicals and hydrogen: A review

Electrochemical conversion of biomass-derived aldehydes into fine chemicals and hydrogen: A review

Efficient MPV reductions of biomass-derived aldehydes and ketones over an assembling zirconium-gallic acid hybrid under mild condition

The utilization of natural renewable resources for the synthesis of catalytic materials and their application for the sustainable production of high value chemicals from lignocellulose is a very attractive topic. Herein, F127 was used as a dispersant to promote the formation of robust organic–inorganic hybrids (Zr5-GAF) of gallic acid (GA) selected as organic ligands with Zr in ethanol for the Meerwein-Ponndorf-Verley reduction of biomass-derived aldehydes and ketones. Multiple characterizations proved that F127 enhanced the connectivity of Zr and GA while effectively increased the specific surface area and pore volume of the catalyst. The addition of F127 shifted the binding energy of Zr and O to higher values and thus obtained more and stronger Lewis acid-base sites. The synthesized Zr5-GAF helped to yield near-quantitative furfuryl alcohol (FA, 94.7%) and a much higher FA production rate than previously reported under mild conditions (100 ℃, 1 h). Moreover, kinetic experiments showed that the reduction activation energy of furfural was as low as 36.04 kJ/mol and Zr5-GAF exhibited good recyclability for at least six reaction cycles. The approach of designing heterogeneous catalytic materials from GA with economical, environmentally friendly and sustainable characteristics has great potential in green chemistry.

Unraveling Electroreductive Mechanisms of Biomass-Derived Aldehydes via Tailoring Interfacial Environments

Unraveling Electroreductive Mechanisms of Biomass-Derived Aldehydes via Tailoring Interfacial Environments

Bipolar Hydrogen Production from Biomass-Derived Aldehydes and Water in Flow Electrolyzers

It is critical to fight against global warming and confine it to a manageable level of +1.5°C by curbing CO2 emissions, eventually achieving zero net emissions by 2050. This target will involve significant efforts from all industry sectors and require renewable energy storage and conversion, most of which are heavily rely on clean hydrogen production. Water electrolysis, producing hydrogen and oxygen from water and electricity, is a promising route to the decarbonization of industry and transportation. The main source of energy loss in water electrolysis is the unfavorable thermodynamics (standard potential of 1.23 V vs. NHE) and slow kinetics of oxygen evolution reaction (OER). These challenges motivate us to design efficient paired electrolysis systems to substitute OER. In this work, we demonstrate an efficient bipolar hydrogen production system that combines cathodic hydrogen evolution from water and anodic hydrogen generation from aldehyde oxidation, at a low voltage (~0.1V) with co-generation of high valuable carboxylic acid. We used furfural as the model aldehyde, a biomass-derived compound that is produced on a large scale, currently on a scale of 0.43 million tons/year. Unlike conventional combined systems for hydrogen production that require high voltage (> 1.0 V) and are limited by mass transport (<100 mA cm−2) of reactants, this study doubled the hydrogen production rate, obtained industrial-level current density (e.g. 390 mA cm−2, 0.6V), and achieved economic viability ($2.51/kg of H2). These achievements benefit from a thermodynamically favorable hydrogen production pathway from aldehyde, facile kinetics on porous Cu-based catalysts, efficient mass transport in flow cells, and inexpensive size-exclusive separators. The successful implementation of such an energy-efficient process will impact future low-carbon hydrogen production and distributed chemical manufacturing.

Enhanced sorption of carbonyl groups by zirconium hydroxide modified with polydopamine for highly selective production of alcohols via MPV reduction under mild conditions

Enhanced sorption of catalysts to enrich and activate carbonyl substrates for highly selective production of the corresponding alcohols is an important means to boost the reaction rate. Based on the properties of dopamine polymerization under alkaline conditions, three mixtures of Zr and polydopamine with different structures were in situ synthesized by adjusting the feeding order of the raw materials. The three catalysts exhibited differences in physical adsorption capacity by N2 isothermal adsorption experiments, and the introduction of polydopamine strengthened the chemisorption of furfural by zirconium hydroxide as proved by ATR-IR. Zr-PDAE showed excellent MPV reduction ability for a variety of biomass-derived aldehydes and ketones, in which 93.9 % furfural conversion and 98.2 % furfural selectivity were achieved at 120 °C for 1 h. The modification of the selective adsorption of carbonyl substrate capacity is beneficial for the value-added conversion of biomass resources.

Insight into the production of aviation fuel by aldol condensation of biomass-derived aldehydes and ketones followed by hydrogenation

Insight into the production of aviation fuel by aldol condensation of biomass-derived aldehydes and ketones followed by hydrogenation