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Catalyst development for upgrading bio-based chemicals towards primary amines has increasingly attracted owing to their applications in the pharmaceutical and polymer industries. The surface acidic sites in metal oxide-based catalysts play a key role in the reductive amination of aldehydes/ketones involving H 2 and NH 3 ; however, the crucial role of the type of surface acidic species and their strength remains unclear. Herein, this study exhibits the catalytic reductive amination of furfural (FUR) to furfurylamine (FUA) with Ru supported on tetragonal (Ru/T-ZrO 2 ) and monoclinic (Ru/M-ZrO 2 ) ZrO 2 . Ru/T-ZrO 2 exhibited an 11.8-fold higher rate of reductive amination than Ru/M-ZrO 2 , giving a quantitative yield of FUA (99 %) at 80 °C in 2.5 h and is recyclable up to four runs. Catalyst surface investigation using spectroscopic techniques, like X-ray photoelectron, electron paramagnetic resonance, and Raman, confirm higher oxygen vacancy sites (1.6 times) on the surface of Ru/T-ZrO 2 compared to Ru/M-ZrO 2 . Moreover, in-situ NH 3 -diffuse reflectance infrared Fourier transform spectroscopy studies display that Ru/T-ZrO 2 has more moderate Bronsted acidic sites (surface H-bonded hydroxyl groups) than Ru/M-ZrO 2 . Further, the controlled experiments and poisoning studies with KSCN and 2,6-lutidine suggest the crucial role of O v sites (Lewis acidic sites) and surface hydroxyl groups (Bronsted acidic sites) for selective FUA formation., (© 2024 Wiley-VCH GmbH.)

The present study focused on developing a stable basic MnOx support for Ru (RuMn) for the efficient oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in water in the absence of an external base. A series of MnOx supports, synthesized via hydrothermal approach using urea as precipitant, was prepared by thermal treatment at various temperatures (300-800 °C) before doping with Ru. The RuMn-2 (1 wt % Ru, MnOx calcined at 400 °C) possessed a large number of basic sites (1.72 mmol g -1 ) based on CO 2 temperature-programmed desorption analysis, affording an FDCA yield of 87 % with a turnover frequency of 22 h -1 . Transmission electron microscopy energy-dispersive X-ray spectroscopy elemental mapping of RuMn-2 showed a high dispersion of Ru over the surface of MnOx, contributing to the efficient HMF oxidation. Moreover, X-ray diffraction, X-ray photoelectron spectroscopy, and H 2 temperature-programmed reduction indicated that the predominant MnO 2 phase (ϵ-MnO 2 ) played a vital role in HMF oxidation. RuMn-2 was recyclable for up to four runs without significant loss in the activity and retained its structural integrity., (© 2022 Wiley-VCH GmbH.)

One-pot synthesis of sustainable primary amines by catalytic reductive amination of bio-based carbonyl compounds with NH 3 and H 2 is emerging as a promising and robust approach. The primary amines, especially furfuryl amine (FUA) derived from furfural (FUR), with a wide range of applications from pharmaceuticals to agrochemicals, have attracted much attention due to their versatility. This Review is majorly comprised of two segments on the reductive amination of FUR to FUA, one with precious (Ru, Pd, Rh) and the other with non-precious (Co, Ni) metals on different supports and in various solvent systems in the presence of NH 3 and H 2 . The active metal sites generated on multiple supports are accentuated with experimental evidence based on CO-diffuse reflectance infrared Fourier-transform spectroscopy, H 2 temperature-programmed reduction, X-ray photoelectron spectroscopy, and calorimetry. Moreover, this Review comprehensively describes the role of acidic and basic support for the metal on the yield of FUA. Overall, this Review provides an insight into how to design and develop an efficiently robust catalyst for the selective reductive amination of a broad spectrum of carbonyl compounds to corresponding amines., (© 2022 Wiley-VCH GmbH.)

Shifting from petroleum-based resources to inedible biomass for the production of valuable chemicals and fuels is one of the significant aspects in sustainable chemistry for realizing the sustainable development of our society. Various renowned biobased platform molecules, such as 5-hydroxymethylfurfural, furfural, levulinic acid, and lactic acid, are successfully accessible from the transformation of biobased sugars. To achieve the specific reaction routes, heterogeneous nanoporous acidic materials have served as promising catalysts for the conversion of bio-sugars in the past decade. This Review summarizes advances in various nanoporous acidic materials for bio-sugar conversion, in which the number of carbon atoms is variable and controllable with the assistance of the switchable structure of nanoporous materials. The major focus of this Review is on possible reaction pathways/mechanisms and the relationships between catalyst structure and catalytic performance. Moreover, representative examples of catalytic upgrading of biobased platform molecules to biochemicals and fuels through selective C-C cleavage and coupling strategies over nanoporous acidic materials are also discussed., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

5-Hydroxymethylfurfural (HMF) is one of the versatile platform molecules that can be derived from biomass, and a promising starting substrate for producing 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). DFF is a platform chemical with applications in pharmaceuticals, macrocyclic ligands, and functional polymeric materials. Importantly, FDCA is being considered as a potential alternative to replace terephthalic acid for producing the bioplastic polyethylene furanoate, instead of polyethylene terephthalate, by blending with ethylene glycol. A significant number of studies have focused on the oxidation of HMF to FDCA with metal-containing heterogeneous catalysts in both aqueous and organic media in the presence of peroxides/air/molecular oxygen as the oxidant. In this regard, articles have recently been published related to HMF oxidation with base (nonprecious)-metal-containing catalysts that exhibit appealing activity towards DFF or FDCA in terms of yield. Thus, this Minireview focuses on recent developments in efficient transformations of HMF to DFF and FDCA with base-metal-containing heterogeneous catalysts in aqueous and organic media. This review further focuses on the direct transformation of glucose/fructose to DFF and/or FDCA with nonprecious-metal-containing catalysts in various solvents. Photocatalytic approaches for HMF oxidation with nonprecious metal- containing catalysts are also briefly discussed., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO 2 in methanol at 220 °C and 50 bar H 2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO 2 instead of Fe/ZrO 2 alone. Moreover, the ZrO 2 support contributed to improve the yield as a phase transition of ZrO 2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO 2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO 2 also effectively catalyzed methanol reforming to produce H 2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N 2 instead of H 2 . Fe-Ni/ZrO 2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO 2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Biofuranic compounds, typically derived from C 5 and C 6 carbohydrates, have been extensively studied as promising alternatives to chemicals based on fossil resources. The present work reports the simple assembly of biobased 2,5-furandicarboxylic acid (FDCA) with different metal ions to prepare a range of metal-FDCA hybrids under hydrothermal conditions. The hybrid materials were demonstrated to have porous structure and acid-base bifunctionality. Zr-FDCA-T, in particular, showed a microspheric structure, high thermostability (ca. 400 °C), average pore diameters of approximately 4.7 nm, large density, moderate strength of Lewis-base/acid centers (ca. 1.4 mmol g -1 ), and a small number of Brønsted-acid sites. This material afforded almost quantitative yields of biofuranic alcohols from the corresponding aldehydes under mild conditions through catalytic transfer hydrogenation (CTH). Isotopic 1 H NMR spectroscopy and kinetic studies verified that direct hydride transfer was the dominant pathway and rate-determining step of the CTH. Importantly, the Zr-FDCA-T microspheres could be recycled with no decrease in catalytic performance and little leaching of active sites. Moreover, good yields of C 5 (i.e., furfural) or C 4 products [i.e., maleic acid and 2(5H)-furanone] could be obtained from furfuryl alcohol without oxidation of the furan ring over these metal-FDCA hybrids. The content and ratio of Lewis-acid/base sites were demonstrated to dominantly affect the catalytic performance of these redox reactions., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A highly selective self-condensation of glycolaldehyde to different C 4 molecules has been achieved using Lewis acidic stannosilicate catalysts in water at moderate temperatures (40-100 °C). The medium-sized zeolite pores (10-membered ring framework) in Sn-MFI facilitate the formation of tetrose sugars while hindering consecutive aldol reactions leading to hexose sugars. High yields of tetrose sugars (74 %) with minor amounts of vinyl glycolic acid (VGA), an α-hydroxyacid, are obtained using Sn-MFI with selectivities towards C 4 products reaching 97 %. Tin catalysts having large pores or no pore structure (Sn-Beta, Sn-MCM-41, Sn-SBA-15, tin chloride) led to lower selectivities for C 4 sugars due to formation of hexose sugars. In the case of Sn-Beta, VGA is the main product (30 %), illustrating differences in selectivity of the Sn sites in the different frameworks. Under optimized conditions, GA can undergo further conversion, leading to yields of up to 44 % of VGA using Sn-MFI in water. The use of Sn-MFI offers multiple possibilities for valorization of biomass-derived GA in water under mild conditions selectively producing C 4 molecules., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol-water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl xyluloside (step 1) followed by hydrolysis after water addition to form additional xylulose (step 2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1 h of reaction at 100 °C was 39%. After water hydrolysis in the second reaction step, the yield increased to 47%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ionic liquids (ILs) comprised of ammonium cations and anions of naturally occurring amino acids containing an additional amine group (e.g., lysine, histidine, asparagine, and glutamine) were examined as high-capacity absorbents for CO2. An absorption capacity of 2.1 mol CO2 per mol of IL (3.5 mol CO2 per kg IL, 13.1 wt% CO2) was measured for [N66614][Lys] at ambient temperature and about 1 mol CO2 per mol of IL at 808C (under 1 bar of CO2). This demonstrated that desorption is possible under CO2-rich conditions by temperature-swing absorption; three consecutive sorption cycles were performed with the IL. The mechanistic and kinetic study of the absorption process was further substantiated by NMR spectroscopy and in situ attenuated total reflectance FTIR for [N66614][Lys] and the homologous phosphonium-based IL [P66614][Lys]. This study revealed that carbamic acid was formed with CO2 in both ILs by chemisorption; however, the amino acid–carboxyl groups on the anion played an important—but different—catalytic role for the sorption kinetics in the two ILs. The origin of the cationic effect is speculated to be correlated with the strength of the ion interactions in the two ILs.