Selective electrocatalytic hydrogenation of lignocellulose-derived 5-hydroxymethylfurfural with superior productivities
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ABSTRACT:
SUBMITTER: Zhang D
PROVIDER: S-EPMC10579428 | biostudies-literature | 2023 Sep
REPOSITORIES: biostudies-literature
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Project description:Converting biomass-derived 5-hydroxymethylfurfural (HMF) into high-valued 2,5-dihydroxymethylfurfural (DHMF) via electrocatalytic hydrogenation (ECH) technology has been widely regarded as one of the most economical and eco-friendly routes. The high selectivity and activity depend on the reasonable regulation of the adsorption and activation of adsorbed hydrogen (H*) and HMF on the surface of the electrocatalyst. Herein, we report nanoflower-like CuFe-based electrocatalysts on copper foam (CF) substrates (CuFeOx/CF). DHMF was achieved on the optimal CuFeOx/CF with a selectivity of 93.3 % and a yield of 90.1 %. The H*, HMF and product were observed by in situ attuned total reflection Fourier transform infrared spectroscopy (ATR-FTIR). Moreover, in situ Raman spectra discloses the reconstruction of catalyst into CuFe-bimetal with low valence state. Density functional theory (DFT) calculations demonstrate that introducing Fe plays a role in regulating the electronic structure of Cu sites, which facilitate the generation of H* and adsorption of HMF, thus hampering the occurrence of dimerization. This study provides an innovative idea for the rational design of non-precious bimetallic electrocatalysts for ECH to produce high-valued chemicals.
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Project description:The catalytic transformation of bio-derived compounds, specifically 5-hydroxymethylfurfural (HMF), into value-added chemicals may provide sustainable alternatives to crude oil and natural gas-based products. HMF can be obtained from fructose and successfully converted to 2,5-diformylfuran (DFF) by an environmentally friendly organic electrosynthesis performed in an ElectraSyn reactor, using cost-effective and sustainable graphite (anode) and stainless-steel (cathode) electrodes in an undivided cell, eliminating the need for conventional precious metal electrodes. In this work, the electrocatalysis of HMF is performed by using green solvents such as acetonitrile, γ-valerolactone, as well as PolarClean, which is used in electrocatalysis for the first time. The reaction parameters and the synergistic effects of the TEMPO catalyst and 2,6-lutidine base are explored both experimentally and through computation modeling. The molecular design and synthesis of a size-enlarged C3 -symmetric tris-TEMPO catalyst are also performed to facilitate a sustainable reaction work-up through nanofiltration. The obtained performance is then compared with those obtained by heterogeneous TEMPO alternatives recovered by using an external magnetic field and microfiltration. Results show that this new method of electrocatalytic oxidation of HMF to DFF can be achieved with excellent selectivity, good yield, and excellent catalyst recovery.
| S-EPMC7318667 | biostudies-literature
Project description:Electrocatalytic hydrogenation of lignocellulosic bio-oil to value-added chemicals offers an attractive avenue to use the increasing intermittent renewable electricity and biomass-derived feedstocks. However, to date the partial current densities to target products of these reactions are lower than those needed for industrial-scale productivity, which limits its prospects. Here we report a flow-cell system equipped with a Rh diffusion electrode to hydrogenate lignocellulose-derived aromatic monomers, such as furans and lignin monomers, to value-added chemicals. We achieve high faradaic efficiencies up to 64% at industrial-scale current densities of 300-500 mA cm-2, representing high productivities to target products. A screening of electrocatalysts indicates that only by highly-electrolyte-permeable Rh diffusion electrodes are we able to unite current density with faradaic efficiency. We apply in-situ infrared reflection-absorption spectroscopy to investigate the electrode-potential-dependent reaction pathways and intermediates, confirming a wide potential window for efficient electrocatalytic hydrogenation of lignocellulose-derived aromatics to target products.
| S-EPMC10636212 | biostudies-literature
Project description:Alkynols semi-hydrogenation is a critical industrial process as the product, alkenols, have extensive applications in chemistry and life sciences. However, this class of reactions is plagued by the use of high-pressure hydrogen, Pd-based catalysts, and low efficiency of the contemporary thermocatalytic process. Here, we report an electrocatalytic approach for selectively hydrogenating alkynols to alkenols under ambient conditions. For representative 2-methyl-3-butene-2-ol, Cu nanoarrays derived electrochemically from CuO, achieve a high partial current density of 750 mA cm-2 and specific selectivity of 97% at -0.88 V vs. reversible hydrogen electrode in alkaline solution. Even in a large two-electrode flow electrolyser, the Cu nanoarrays deliver a single-pass alkynol conversion of 93% with continuous production of 2-methyl-3-butene-2-ol at a rate of ~169 g gCu-1 h-1. Theoretical and in situ electrochemical infrared investigations reveal that the semi-hydrogenation performance is enhanced by exothermic alkynol adsorption and alkenol desorption on the Cu surfaces. Furthermore, this electrocatalytic semi-hydrogenation strategy is shown to be applicable to a variety of alkynol substrates.
| S-EPMC10027872 | biostudies-literature
Project description:Electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR), as a clean biorefinery process, promotes a circular economy with value-added products. In HMFOR, the intrinsic catalytic activity and charge transfer mechanisms are crucial. Herein, nickel, co-deposited with phosphorus (Ni-P), attains superior electrocatalytic performance compared with Ni and its oxyhydroxides for the HMFOR. Such electrocatalytic activity of the Ni-P catalyst is attributed to the high oxidation state of surface Ni species, supported by the bulk Ni-P component. An unprecedented charge storing capacity enabled by the bulk Ni-P material maintains the spontaneous reaction between HMF and Ni3+ species to achieve a current density of 10 mA/cm2 normalized by the electrochemical active surface area at a low potential of 1.42 V vs RHE, reaching a 97% Faradaic efficiency toward 2,5-furandicarboxylic acid. This work, for the first time, sheds light on the importance of the electrode bulk material by showcasing the HMFOR via the Ni-P catalyst incorporating a charge-holding bulk component.
| S-EPMC9356110 | biostudies-literature
Project description:Simultaneous electrocatalytic reduction and oxidation of 5-hydroxymethylfurfural (HMF) is crucial for biomass refineries. Herein, we report the unprecedentedly high efficiency of the nearly complete conversion of biomass-derived HMF to value-added products, achieving >95% selectivity at -0.4 V vs RHE by pairing electrocatalytic reduction and oxidation (PERO) reactions in a single electrochemical cell. At the cathode, we achieved 99% conversion of HMF to 2,5-dihydroxymethylfuran (DHMF) in ∼99% yield under mild conditions using a PtRu alloy. At the anode, we observed 99% conversion of HMF, nearly perfect selectivity for the oxidative product 2,5-furandicarboxylic acid (FDCA), and 100% Faradaic efficiency on a NiCo(OOH) x nanosheets electrode. The kinetic isotope effect demonstrated that the rate-controlled step was a proton-independent electron transfer process, with minimal impact from substrate concentration variations. After assembling the synchronous reaction cell, the PERO of HMF generated high yields of DHMF (94%) and FDCA (86%), achieving a combined electron efficiency of 131%, nearly doubling the performance of uncoupled cells. This superior performance was attributed to the efficient generation of H* on the PtRu alloy for reduction, alongside the OH* active sites on the NiCo(OOH) x nanosheets electrode for oxidation. This research provides a promising strategy for the sustainable electrocatalytic upgrading of biomass-derived chemicals.
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Project description:The electrochemical conversion of 5-Hydroxymethylfurfural, especially its reduction, is an attractive green production pathway for carbonaceous e-chemicals. We demonstrate the reduction of 5-Hydroxymethylfurfural to 5-Methylfurfurylalcohol under strongly alkaline reaction environments over oxide-derived Cu bimetallic electrocatalysts. We investigate whether and how the surface catalysis of the MOx phases tune the catalytic selectivity of oxide-derived Cu with respect to the 2-electron hydrogenation to 2.5-Bishydroxymethylfuran and the (2 + 2)-electron hydrogenation/hydrogenolysis to 5-Methylfurfurylalcohol. We provide evidence for a kinetic competition between the evolution of H2 and the 2-electron hydrogenolysis of 2.5-Bishydroxymethylfuran to 5-Methylfurfurylalcohol and discuss its mechanistic implications. Finally, we demonstrate that the ability to conduct 5-Hydroxymethylfurfural reduction to 5-Methylfurfurylalcohol in alkaline conditions over oxide-derived Cu/MOx Cu foam electrodes enable an efficiently operating alkaline exchange membranes electrolyzer, in which the cathodic 5-Hydroxymethylfurfural valorization is coupled to either alkaline oxygen evolution anode or to oxidative 5-Hydroxymethylfurfural valorization.
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Project description:Lignocellulosic biomass is the only renewable source of carbon for the chemical industry. Alkylmethoxyphenols can be obtained in good yield from woody biomass by reductive fractionation, but these compounds are of limited value for large-scale applications. We present a method to convert lignocellulose-derived alkylmethoxyphenols to phenol that can be easily integrated in the petrochemical industry. The underlying chemistry combines demethoxylation catalyzed by a titania-supported gold nanoparticle catalyst and transalkylation of alkyl groups to a low-value benzene-rich stream promoted by HZSM-5 zeolite. In this way, phenol can be obtained in good yield, and benzene can be upgraded to more valuable propylbenzene, cumene, and toluene. We demonstrate that intimate contact between the two catalyst functions is crucial to transferring the methyl groups from the methoxy functionality to benzene instead of phenol. In a mixed-bed configuration, we achieved a yield of 60% phenol and 15% cresol from 4-propylguaiacol in a continuous one-step reaction at 350 °C at a weight hourly space velocity of ∼40 h-1.
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Project description:A new type of biomass-based liquid fuel, 2,5-dimethylfuran (DMF), has attracted significant attention owing to its unique physical properties and carbon neutrality. It can be obtained from the hydrogenation of 5-hydroxymethylfurfural (HMF), an important biomass platform compound. In this study, we developed a nitrogen-doped carbon-confined CuCo bimetallic catalyst with a popcorn-like structure for the selective hydrogenation of HMF with high efficiency and adequate stability. Under optimized conditions, 100% HMF conversion and 93.7% DMF selectivity were achieved. The structure of the catalyst was characterized using XRD, XPS, SEM, and TEM. It was observed that carbon spheres, which were covered by nitrogen-doped carbon nanotubes, uniformly formed, while metal particles were confined in the nitrogen-doped carbon nanotubes. The popcorn-like structure exhibited a larger surface area and provided more contact sites, while the confined metal particles were the main active sites. The synergistic effect between Cu and Co was beneficial for DMF selectivity.
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Project description:ZrO2 heterophase structure nanocrystals (HSNCs) were synthesized with tunable ratios of monoclinic ZrO2 (m-ZrO2) to tetragonal ZrO2 (t-ZrO2). The phase mole ratio of m-ZrO2 versus t-ZrO2 in ZrO2 HSNCs was tuned from 40% to 100%. The concentration of the surface hydroxyl groups on m-ZrO2 is higher than that on t-ZrO2. ZrO2 HSNCs have different surface hydroxyl groups on two crystalline phases. This creates more intimate synergistic effects than their single-phase counterparts. The ZrO2 HSNCs were used as effective supports to fabricate heterophase-structured Ru/ZrO2 catalysts for benzene-selective hydrogenation. The excellent catalytic performance including high activity and selectivity is attributed to the heterogeneous strong/weak hydrophilic interface and water layer formed at the m-ZrO2/t-ZrO2 catalyst junction.
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