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      Editorial: Sustainable catalytic production of bio-based heteroatom-containing compounds — volume II

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          Abstract

          Fossil-based heteroatom-containing compounds are crucial core scaffolds or key intermediates in a wide range of pharmaceutical molecules, fiber dyes and printing ink (Li et al., 2019a; Wu et al., 2020; Wu et al., 2021), which can also be directly used as solvents, surfactants, and so on (Li et al., 2019b; Wu et al., 2019; Xu et al., 2019). However, mainly owing to the dependence and overuse of fossil source, the environmental pollution/deterioration and greenhouse effect are becoming increasingly prominent. In this regard, sustainability is deemed as a key parameter for the future of producing heteroatom-containing compounds and environmental enhancement, which not only requires the replacement of the fossil fuel feedstocks by other renewable resources (e.g., non-food biomass), but also needs the adoption of circular utilisation methods to prevent leakage of any ingredient into the environment (Iglesias et al., 2020). This Research Topic is Volume II of a series, and here we present a collection of original research and review articles (20 papers in total) with topics on green and sustainable chemistry, including catalytic conversion of biomass feedstocks (Liu et al., Zhu et al., Liu et al., Zhang et al., Sun et al., Yao et al., Zhou et al., Zhao et al., Yang et al., and Zhou et al.), biodiesel production (Wu et al., Zhang et al., and Liu et al.), and green synthesis of heteroatom-containing bioactive compounds and functional materials (Wang et al., Pan et al., Chen et al., Pan et al., Zhang et al., and Bao et al.). Also, the Research Topic provides interesting insights into the green photocatalysis of organic pollutants (Zhang et al.). Original research paper of Zhou et al. reports the controllable preparation of three kinds of Fe-based composite catalysts with different Fe loadings for efficient hydrogen production from biomass steam gasification. When the mass fraction of loading is 10%, Fe species are well dispersed on the carrier, affording a high gas yield of 60.4% (with 42.2% hydrogen proportion). Zhang et al. use glycerol waste to comparatively evaluate the ameliorative effect on lignocellulose under microwave or conventional heating method. During fast pyrolysis, levoglucosan produced from microwave-treated samples (32.9%) was far more selective than the conventional heating group (18.8%), and the content of aldehydes (high toxicity to the downstream fermentation) after glycerol waste and microwave pretreatment was decreased by 2.5 times compared with the untreated counterpart. In addition to directly using raw biomass resources, simple sugars like fructose can be efficiently converted to 5-hydroxymethylfurfural (up to 82% yield) by dehydration over a stable Ti-doped SBA-15 catalyst in DMSO at 140°C for 1 h (Zhu et al.), or to 5-ethoxymethylfurfural (80.4% yield) by cascade dehydration-etherification using a UIO-66-SO3H catalyst in ethanol under the same thermal conditions (Zhao et al.). Zhang et al. manufacture a biomass-based solid acid catalyst (SiO2@Cs-SO3H) with a large specific surface area (21.82 m2/g) and acidity (3.47 mmol/g) using renewable chitosan as raw material through sulfonation procedure under relatively mild conditions, which is active for esterification of oleic acid and methanol to produce biodiesel (98.2% yield). The work of Chen et al. reports an unprecedented inactivation process of the indanol-derived NHC catalysts bearing N-C6F5 groups, giving an unexpected multi-cyclic complex product from the 3-component reaction with 1-methylcyclopropyl-carbaldehyde, 2,2,2-trifluoroacetophenone and the NHC catalyst. Pan et al. develop an acid-catalyzed 2-alkylation of indole molecules catalyzed by traceless HI, and 2,3-disubstituted indole molecules bearing congested tertiary carbon centers are obtained in moderate to good yields. Some functional catalytic materials such as hierarchical porous SAPO-34 (Wang et al.), bimetallic Zn-Zr metal-organic framework (Zhang et al.), and graphene oxide-silver nanoparticles composite (Bao et al.) are prepared in sustainable ways, and found to be efficient for the synthesis of value-added chemicals (e.g., 4,6-dimethyldibenzothiophene) or degradation of organic pollutants. This Research Topic features several review articles with distinct scopes (Liu et al., Sun et al., Zhou et al., Yang et al., Yao et al., Liu et al., Wu et al., Liu et al., Pan et al., and Zhang et al.). Liu et al. review the application of recyclable heterogeneous non-noble Zr/Hf-containing catalysts (e.g., Zr/Hf-containing metal oxides, supported materials, zeolites, metal organic frameworks, metal organic hybrids) with acid-base bifunctionality for catalytic transfer hydrogenation using the safe liquid hydrogen donor, with emphasis on evaluating the reaction mechanisms and conversion pathways. In a more detailed manner, the research progress of catalytic synthesis of γ-valerolactone from furfural by Zr/Hf-based catalysts is reviewed by Sun et al., and the effects and regulation approaches of Lewis acid-base and Brønsted acid sites in the catalysts on each steps in the reaction process are discussed. Zhou et al. reveal the significance and potential of using titanate nanotubes-based materials as sustainable and environmentally benign solid catalysts/supports for synthesis of various bio-based chemicals, such as glycerol-derived solketal, jet fuel range alkanes precursors, biomass-derived esters, aldehydes, and aromatic compounds. Yang et al. propose the research development trend for improving the institutional mechanism of the utilization of crop straw resources, strengthening technology research and development, exploring the economic model of green cycle agriculture, accelerating the construction of the industrial system, and designing new paths of resource utilization in multiple ways. Yao et al. mainly review some latest studies about the conversion of cellulose to 5-hydroxymethylfurfural catalyzed by solid acids with Brønsted and/or Lewis acidic sites, such as sulfonated solid acids, carbon-based acids, and zeolites. Liu et al. summarize the mechanisms of several important processes of producing 5-ethoxymethylfurfural from lignocellulosic biomass-derived sugars and the research progress of the developed acid catalysts. In addition, advancements in tobacco (Nicotiana tabacum L.) seed oils (Wu et al.) and lipid extraction from microalgae using green solvents (Liu et al.) for biodiesel production are also collected. For some structurally somplex natural products such as sex pheromones (Pan et al.), and momilactones and related 9β-H pimarane skeleton (Zhang et al.), the recent advances in their synthetic strategies with the involved challenges are overviewed. We wish this Research Topic attracts interested colleagues, enlightening more eco-friendly and sustainable synthetic procedures, shedding light on renewed catalytic strategies and routes developed for the production of bio-based heteroatom-containing compounds, and providing enthusiasm in research and studies. Enjoy its reading!

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          Most cited references7

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          Advances in catalytic routes for the production of carboxylic acids from biomass: a step forward for sustainable polymers

          This review revises the advances in the chemocatalytic processes for producing renewable carboxylic acids for the synthesis of bio-based polymers and proposes the actions to overcome the problems threatening their technical and economic viability. Polymers are ubiquitously present in our daily life because they can meet a wide range of needs and fields of applications. This success, based on an irresponsible linear consumption of plastics and the access to cheap oil, is creating serious environmental problems. Two lines of actions are needed to cope with them: to adopt a circular consumption of plastics and to produce renewable carbon-neutral monomers. This review analyses the recent advances in the chemocatalytic processes for producing biomass-derived carboxylic acids. These renewable carboxylic acids are involved in the synthesis of relevant general purpose and specialty polyesters and polyamides; some of them are currently derived from oil, while others can become surrogates of petrochemical polymers due to their excellent performance properties. Polyesters and polyamides are very suitable to be depolymerised to other valuable chemicals or to their constituent monomers, what facilitates the circular reutilisation of these monomers. Different types of carboxylic acids have been included in this review: monocarboxylic acids (like glycolic, lactic, hydroxypropanoic, methyl vinyl glycolic, methyl-4-methoxy-2-hydroxybutanoic, 2,5-dihydroxypent-3-enoic, 2,5,6-trihydroxyhex-3-enoic acids, diphenolic, acrylic and δ-amino levulinic acids), dicarboxylic acids (2,5-furandicarboxylic, maleic, succinic, adipic and terephthalic acids) and sugar acids (like gluconic and glucaric acids). The review evaluates the technology status and the advantages and drawbacks of each route in terms of feedstock, reaction pathways, catalysts and economic and environmental evaluation. The prospects and the new research that should be undertaken to overcome the main problems threatening their economic viability or the weaknesses that prevent their commercial implementation have also been underlined.
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            N-formyl-stabilizing quasi-catalytic species afford rapid and selective solvent-free amination of biomass-derived feedstocks

            Nitrogen-containing compounds, especially primary amines, are vital building blocks in nature and industry. Herein, a protocol is developed that shows in situ formed N-formyl quasi-catalytic species afford highly selective synthesis of formamides or amines with controllable levels from a variety of aldehyde- and ketone-derived platform chemical substrates under solvent-free conditions. Up to 99% yields of mono-substituted formamides are obtained in 3 min. The C-N bond formation and N-formyl species are prevalent in the cascade reaction sequence. Kinetic and isotope labeling experiments explicitly demonstrate that the C-N bond is activated for subsequent hydrogenation, in which formic acid acts as acid catalyst, hydrogen donor and as N-formyl species source that stabilize amine intermediates elucidated with density functional theory. The protocol provides access to imides from aldehydes, ketones, carboxylic acids, and mixed-substrates, requires no special catalysts, solvents or techniques and provides new avenues for amination chemistry.
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              Hydrothermal amination of biomass to nitrogenous chemicals

              This review presents the conversion routes, processing strategies, state-of-the-art technical advances, challenges and perspectives in hydrothermal amination of N -rich biomass sources and N -free biomass feedstocks to nitrogenous chemicals. Biomass is the most abundant and low-cost renewable source for the production of value-added nitrogen-containing compounds. However, a large amount of water exists in natural biomass and relevant bio-derivatives, which often need to be removed prior to conducting valorization processes. Direct use of wet biomass and bio-derivatives as feedstocks definitely avoids energy consumption of drying processes, in which water acts as a reactive medium and is friendly to the environment and reaction devices. Hydrothermal amination of wet biomass feedstocks is thus an attractive technical strategy for producing nitrogen-containing compounds. This review summarizes state-of-the-art technologies in hydrothermal amination of natural biomass, bio-polymeric derivatives, and bio-based platform molecules with or without nitrogenous species into organonitrogen chemicals. Efforts are made to shed light on conversion routes and economic/environmental impacts of biomass hydrothermal amination. Challenges and perspectives on the large-scale production of biomass-derived nitrogenous compounds are also put forward.
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                Author and article information

                Contributors
                Journal
                Front Chem
                Front Chem
                Front. Chem.
                Frontiers in Chemistry
                Frontiers Media S.A.
                2296-2646
                05 September 2022
                2022
                : 10
                : 1008895
                Affiliations
                [1] 1 State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering , Key Laboratory of Green Pesticide and Agricultural Bioengineering , Ministry of Education , State-Local Joint Laboratory for Comprehensive Utilization of Biomass , Center for R&D of Fine Chemicals , Guizhou University , Guiyang, China
                [2] 2 School of Chemistry , Xi’an Key Laboratory of Sustainable Energy Materials Chemistry , State Key Laboratory of Electrical Insulation and Power Equipment , Xi’an Jiaotong University , Xi’an, China
                Author notes

                Edited and reviewed by: Valeria Conte, University of Rome Tor Vergata, Italy

                *Correspondence: Hu Li, hli13@ 123456gzu.edu.cn ; Song Yang, jhzx.msm@ 123456gmail.com

                This article was submitted to Green and Sustainable Chemistry, a section of the journal Frontiers in Chemistry

                Article
                1008895
                10.3389/fchem.2022.1008895
                9484520
                126becb6-48f6-4e7c-91f4-84b30cdb2e4a
                Copyright © 2022 Huang, Li, Su and Yang.

                This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

                History
                : 01 August 2022
                : 12 August 2022
                Categories
                Chemistry
                Editorial

                sustainable chemistry,biomass conversion,catalytic mechanism,biorefinery,biofuels

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