Selective C
O bond activation of biomass-derived γ-valerolactone to biofuels over MFI-mediated Co-based synergetic catalysts
Introduction
With the depletion of fossil resources, efficiently catalytic conversion of the renewable biomass resources to alternative energy carriers has been widely explored [1], [2], [3]. However, precisely driving specific reaction channels of multifunctional molecules to obtain target products entails a challenging selectivity problem in the conversion of biomass-derived substrates to valuable biofuels and chemicals [4], [5]. For example, as one of the most important lignocellulosic-derived platform compounds, γ-valerolactone (GVL) has been identified with potential impact as a feedstock for utilization of non-petroleum resources to supply sustainable energy for the carbon-neutral economy [6], [7], [8]. Yet, highly oriented-upgrading of GVL with a prerequisite ring-opening step requires but suffers from precisely activating specific ring C-O bonds [9], [10], [11], [12], wherein the cleavage of γ-carbon ring-oxygen bond with subsequent hydrogenation and esterification steps leads to the generation of valeric biofuels (valeric acid and valerate esters) [11], whereas the conversion of GVL to pentane biofuel proceeds in the breaking of carbonyl-carbon ring-oxygen bond and further multi-hydrodeoxygenation reactions [12]. Therefore, designing novel catalytic systems with characteristics of selectively triggering specific ring C-O bonds activation in GVL ring-opening to exercise highly selectivity control toward desired chemical value chains provide a promising, yet difficult-to-achieve strategy, which are the research cores of GVL chemistry.
Motivated by accumulated evidence that demonstrated the efficient synergetic catalysis between metal and acid sites in enhancing the catalytic reactivity of various biomass model compounds [13], [14], [15], opportunities arose for developing metal-acid bi/multi-functional catalysts composed of customized and sufficient functionality to control nanoscale features precisely. Compared to other crystalline porous materials, zeolite with well-defined pores/cavities, shape-selectivity and feasible design-ability is of importance in a broad range of chemical industrial processes [16]. Amongst, HZSM-5 zeolite (MFI topology) with adjustable framework acidity, well-ordered microporous structure and outstanding thermal stability is regarded as an ideal support for integrating with metal nanoparticles (MNPs) applying for green chemistry [17], [18]. The supported catalyst (metal/HZSM-5) via loading metal species on HZSM-5 carrier is one of the most classical types of metal-acid bifunctional catalysts, which has been widely investigated and applied to various reactions in the past few decades [19]. Whereas the supported catalysts significantly suffer from metal leaching and sintering during the reaction process, accompanied by the surface area loss and coke formation [20], [21], which underscore a pressing need for novel metal-acid synergetic catalysts design in developing oriented-controllable heterogeneous reactions.
Encapsulating MNPs into HZSM-5 zeolite channels (metal@HZSM-5) shows a great potential to exercise selectivity modulation in recent years [22], [23]. In general, rationally integrating metal components within zeolite can effectively offset their drawbacks and synergize their respective strengths in the selective catalytic process. For example, the distinct substrate-shape/size selectivity involving the controllable formation and diffusion of reaction products in zeolite micropores [24], [25], the predetermined reaction sequence in tandem catalysis via tailoring spatial distribution of the corresponding metal/acid sites [26], and the adjustable local microenvironment (acidic/alkaline/neutral) around MNPs with the resulting unique surface electronic structure and intrinsic selectivities [27]. In addition, the encapsulated-type catalysts not only provide the required metal-acid confined proximity sites to satisfy the “intimacy criterion” in specific catalytic reactions [28], [29], but also strictly limit the metal sizes, making it benefit for the excellent sinter resistance as well as the high mass-transfer efficiency of shuttling reactants/intermediates [30], [31]. However, the research on the discrepancies of metal-acid synergetic catalysis modes over these metal@HZSM-5 versus metal/HZSM-5 composites is still lacking [15], [32], and it is still an open question on how to tune the catalytic selectivity via modulating the metal chemical microenvironments (e.g., zeolite-confined versus zeolite-supported), in particular, for the selectively oriented-valorization of biomass-derived compounds that generally require a specific C-O bond activation mode, such as GVL selective upgrading.
Herein, we reported a selectively catalytic strategy for converting GVL either to valeric or pentane biofuels, based on the MFI-type HZSM-5 zeolite-mediated Co-based synergetic catalysts (Co@HZSM-5 versus Co/HZSM-5). The experimental and characterization data presented here demonstrated that tailoring the chemical microenvironments of metallic Co in HZSM-5 crystal provided diverse metal-acid synergetic catalysis to manipulate the product distribution in GVL upgrading. Density functional theory (DFT) calculations were further implemented to acquire a heightened understanding of the catalytic nature over these two Co-based catalysts by comparing the reaction energies and barriers of potential ring C-O bond activation modes.
Section snippets
Catalyst preparation
Co@HZSM-5 catalyst with zeolite-encapsulated structure was synthesized via an in-situ hydrothermal crystallization method. We chose silica-supported Co3O4 (Co loading of 10 wt%) as Si source and Co source, which was synthesized via an impregnation procedure using Co(NO3)2·6H2O solution and prepared amorphous silica [33], followed by calcining at 400 ℃ for 4 h. Then the metal-containing seed (Co3O4/SiO2) was mixed with tetrapropylammonium hydroxide (TPAOH, structure-directing agent), Al(NO3)3·9H2
Catalyst characterization
Co@HZ5 catalyst was prepared by the in-situ hydrothermal crystallization of gel systems (see the Experimental section for details), wherein the silica from amorphous silica-supported metal precursor was gradually dissolved at a proper rate in the alkaline environment to create zeolite framwork. Meanwhile, Co particles (~9.0 nm proved by TEM in Fig. S3) were served as seeds for the growth of zeolite crystals and successfully encapsulated within HZ5 framework. Various characterizations were
Conclusions
In summary, we reported a selectively catalytic strategy for GVL conversion involving powerful HZSM-5 zeolite-mediated Co-based synergetic catalysts that accomplished the selectivity switching toward either valeric biofuel (via Co@HZ5) or pentane biofuel (via Co/HZ5). Combined experimental and characterizations confirmed that the designed zeolite-encapsulated Co@HZ5 catalyst with highly dispersed and stable Co NPs inside HZ5 crystal exercised diverse metal-acid synergetic catalysis versus the
CRediT authorship contribution statement
Hongtao Wang: Conceptualization, Investigation, Resources, Data curation, Writing – original draft. Writing – review & editing. Qi Wang: Resources. Yawen Tong: Resources. Yushan Wu: Resources. Jiebang Peng: Resources. Xiang-Kui Gu: Supervision, Project administration, Funding acquisition, Resources, Writing – review & editing. Mingyue Ding: Supervision, Project administration, Funding acquisition, Resources, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (21978225, U21A20317), National Key Research and Development Plan of China (2018YFE0125200), Science and Technology program of Shenzhen (JCYJ20190808150418994), and Fundamental Research Fund for the Central Universities (2042021kf0209, 2042021kf0027). The numerical calculations in this paper have been done on the supercomputing system in the Supercomputing Center of Wuhan University.
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2023, Applied Catalysis B: EnvironmentalCitation Excerpt :The problems of energy consumption and environmental destruction are getting worse, the biofuels and chemicals produced using renewable biomass are regarded as promising alternatives and additives to conventional petrochemical products such as diesel, jet-fuel and plasticizer [1–3].