Hydrolysis-condensation Reactions Research Articles

Amphiphilic Bowl-Shaped Janus Particles Prepared via Thiol-Ene Click Reaction for Effective Oil-Water Separation.

Janus particles for oil-water separation have attracted widespread attention in recent years. Herein, we prepared a bowl-shaped Janus particle that could rapidly separate oil and water through a thiol-ene click reaction and selective etching. Firstly, snowman-like composite microspheres based on silica and mercaptopropyl polysilsesquioxane (SiO2@MPSQ) were prepared by a hydrolytic condensation reaction and phase separation, and the effects of the rotational speed and molar ratios on their microscopic morphologies were investigated. Subsequently, bowl-shaped Janus particles with convex hydrophilic and concave oleophilic surfaces were prepared via a thiol-ene click reaction followed by HF etching. Our amphiphilic bowl-shaped Janus particles could remarkably separate micro-sized oil droplets from an n-heptane-water emulsion with a separation efficiency of >98% within 300 s. Based on the experimental and theoretical results, we proposed the underlying mechanism for the coalescence of oil droplets upon the addition of the amphiphilic bowl-shaped Janus particles.

Polymorphic control in titanium dioxide particles.

The hydrolysis-condensation reaction of TiO2 was adapted to the phase inversion temperature (PIT)-nano-emulsion method as a low energy approach to gain control over the size and phase purity of the resulting metal oxide particles. Three different PIT-nano-emulsion syntheses were designed, each one intended to isolate high purity rutile, anatase, and brookite phase particles. Three different emulsion systems were prepared, with a pH of either strongly acidic (H2O : HNO3, pH ∼0.5), moderately acidic (H2O : isopropanol, pH ∼4.5), or alkaline (H2O : NaOH, pH ∼12). PIT-nano-emulsion syntheses of the amorphous TiO2 particles were conducted under these conditions, resulting in average particle diameter distributions of ∼140 d nm (strongly acidic), ∼60 d nm (moderately acidic), and ∼460 d nm (alkaline). Different thermal treatments were performed on the amorphous particles obtained from the PIT-nano-emulsion syntheses. Raman spectroscopy and powder X-ray diffraction (PXRD) were employed to corroborate that the thermally treated particles under H2O : HNO3 (at 850 °C), H2O : NaOH (at 400 °C), and H2O : isopropanol (at 200 °C) yielded highly-pure rutile, anatase, and brookite phases, respectively. Herein, an experimental approach based on the PIT-nano-emulsion method is demonstrated to synthesize phase-controlled TiO2 particles with high purity employing fewer toxic compounds, reducing the quantity of starting materials, and with a minimum energy input, particularly for the almost elusive brookite phase.

High flashover strength and superhydrophobic coatings by constructing porous surface structure

AbstractFlashover is prone to occur in composite insulation structures such as vacuum‐solid and gas‐solid, which are universally employed in high‐voltage power equipment. In this study, a high flashover strength and superhydrophobic coating were proposed by constructing porous surface morphology. Octadecyl trichlorosilane (OTS) particles were prepared by hydrolysis condensation reaction, and thereafter sprayed onto the substrate surface to form a porous and rough surface structure with hundreds of nanometres of dispersed pores and pits. The coating endowed epoxy resin with maximum 44% flashover voltage increase and the superhydrophobic surface with water contact angle of 158.4°. Since the pore size in OTS coating is close to electron mean free path in atmospheric condition, the collisional ionisation can be effectively hindered, which suppresses the micro‐discharge around the triple junction and improves the flashover strength. The present approach provides a new insight for simultaneously improving flashover strength and superhydrophobic properties of dielectric insulation.

Mesoporous aluminas synthesis using carboxylic acids to enhance performance in CO2 adsorption

This work evaluated for the first time the effect of carbon chain size of different carboxylic acids (stearic and caprylic acid) and crystallization temperatures (60, 120, and 180 °C) on the structural, textural, morphological, basic, and mechanism properties of reaction in the synthesis of mesoporous aluminas (meso-Al2O3). Regarding the structure-directing agents (SDA) traditionally used in the synthesis of meso-Al2O3 (i.g. strong acids, strong bases, and synthetic polymers), carboxylic acids are non-toxic, biodegradable compounds of low commercial value, and can be obtained from renewable sources. The physical-chemical characterizations performed, including low and high-angle X-ray diffractometry (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermal analysis (TG/DTG), nitrogen adsorption-desorption, temperature-programmed desorption of carbon dioxide (CO2-TPD), scanning electron microscopy (SEM), and transmission (TEM), confirmed the formation of mesostructured γ-Al2O3. No pore organization was observed, but a system of interconnected channels was provided by the wormhole-like structure. Mesoporous aluminas synthesized at 180 °C showed an increase in structural, textural (higher of 68 % in pore volume and 36% in pore diameter), and basic properties (around 19 %) about materials synthesized at 60 °C. This can be attributed to the increased degree of coordination of the carboxylic acid with aluminum during the hydrolysis-condensation reactions. Furthermore, stearic acid (longer carbon chain carboxylic acid) tends to bend during micellar aggregation, leading to pore sizes 33% smaller than caprylic acid (shorter carbon chain acid). Therefore, the best condition for meso-Al2O3 synthesis was obtained at 180 °C and using caprylic acid (CAP-180 °C) as SDA. The results of CO2 adsorption showed that all materials correlate better with the pseudo-first order model in the entire temperature range studied (10 – 50 °C), suggesting that diffusion through the interface gas-solid (external diffusion) is the limiting step of the adsorption process. The adsorbent CAP-180 °C showed high adsorption capacity (around 134.45 mgCO2/gads at 10 °C under atmospheric pressure) and elevated stability after eight cycles of adsorption-desorption, reaching adsorption capacity superior to other meso-Al2O3.

Fabrication of high-performance thermally conductive and electrically insulating polymer composites with siloxane/multi-walled carbon nanotube core-shell hybrids at low filler content

A battery of siloxane (SiO)/multi-walled carbon nanotube (MWCT) core-shell hybrids are successfully fabricated by encapsulating MWCTs with siloxanes via the hydrolysis-condensation reaction. First, MWCT is treated by the surfactant to improve the surface polarity. Then, the hydrolysis-condensation reaction of tetraethoxysilane (TEOS) and different saline coupling agents is performed on the surface of MWCTs to achieve various core-shell hybrids. These hybrids serve as fillers of epoxy resin (EPR) to prepare high-performance thermally conductive, electrically insulating and strength-enhanced composites at low fillers loadings. The SiO/MWCT/EPR composite possesses high thermal conductivity (0.55 W m−1 K−1, which is 196.7% higher than pure EPR) and excellent electrical insulation (>1012 Ω) at 1 wt% filler loading. The thermal conductivity improvement mechanism for these composites containing SiO/MWCT core-shell hybrids is demonstrated in detail. Moreover, the siloxane encapsulation route for MWCTs significantly declines their electrical conductivity, which greatly upgrades the practical value of as-prepared thermal conductivity composites.

A Thermo-Mechanically Robust Compliant Electrode Based on Surface Modification of Twisted and Coiled Nylon-6 Fiber for Artificial Muscle with Highly Durable Contractile Stroke.

In this paper, we propose a novel and facile methodology to chemically construct a thin and highly compliant metallic electrode onto a twisted and coiled nylon-6 fiber (TCN) with a three-dimensional structure via surface modification of the TCN eliciting gold-sulfur (Au-S) interaction for enabling durable electro-thermally-induced actuation performance of a TCN actuator (TCNA). The surface of the TCN exposed to UV/Ozone plasma was modified to (3-mercaptopropyl)trimethoxysilane (MPTMS) molecules with thiol groups through a hydrolysis-condensation reaction. Thanks to the surface modification inducing strong interaction between gold and sulfur as a formation of covalent bonds, the Au electrode on the MPTMS-TCN exhibited excellent mechanical robustness against adhesion test, simultaneously could allow overall surface of the TCN to be evenly heated without any significant physical damages during repetitive electro-thermal heating tests. Unlike the TCNAs with physically coated metallic electrode, the TCNA with the Au electrode established on the MPTMS-TCN could produce a large and repeatable contractile strain over 12% as lifting a load of 100 g even during 2000 cyclic actuations. Demonstration of the durable electrode for the TCNA can lead to technical advances in artificial muscles for human-assistive devices as well as soft robots those requires long-term stability in operation.

Inflammation Self-Limiting Electrospun Fibrous Tape via Regional Immunity for Deep Soft Tissue Repair.

Overexpression of inflammatory cytokines and chemokines occurs at deep soft tissue injury sites impeding the inflammation self-limiting and impairing the tissue remodeling process. Inspired by the electrostatically extracellular matrix (ECM) binding property of the inflammatory signals, an inflammation self-limiting fibrous tape is designed by covalently modifying the thermosensitive methacrylated gelatin (GelMA) and negatively charged methacrylated heparin (HepMA) hydrogel mixture with proper ratio onto the electrospun fibrous membrane by mild alkali hydrolysis and carboxyl-amino condensation reaction to restore inflammation self-limiting and promote tissue repair via regional immunity regulation. While the GelMA guarantees cell compatibility, the negatively charged HepMA successfully adsorbs the inflammatory cytokines and chemokines by electrostatic interactions and inhibits immune cell migration in vitro. Furthermore, in vivo inflammation self-limiting and regional immunity regulation efficacy is evaluated in a rat abdominal hernia model. Reduced local inflammatory cytokines and chemokines in the early stage and increased angiogenesis and ECM remodeling in the later phase confirm that the tape is an approach to maintain an optimal regional immune activation level after soft tissue injury. Overall, the reported electrospun fibrous tape will find its way into clinical transformation and solve the challenges of deep soft tissue injury.

Fabrication of superhydrophobic/oleophilic starch cryogel via a simple sol-gel immersion process for removing oil from water

Superhydrophobic/oleophilic adsorbents have attracted considerable attention for removing oil spill that poses a serious threat to the aquatic ecosystem. Porous starch–based materials have been proved to have good oil absorption performance, but superhydrophobicity of these materials has not yet been realized. Herein, a superhydrophobic starch-based adsorbent (HTSC) was fabricated through a simple sol–gel immersion process of hexadecyltrimethoxysilane and tetraethyl orthosilicate in the presence of starch cryogel. The adsorbent was simultaneously provided with low surface energy and hierarchical micro/nanostructures via hydrolysis–condensation reaction. HTSC exhibited high water contact angle (>153.0°) and low sliding angle (<8.0°) as well as excellent self-cleaning and anti-fouling properties. The structural support and stable chemical bonding endowed the material with good mechanical and chemical durability. HTSC also possessed reasonable oil adsorption performance (2.6–7.5 g/g), which was dominated by its porosity and followed pseudo-second-order model. Its selective wettability towards oil and water allowed it to be applied for oil removal under water and from the water surface. This novel superhydrophobic starch–based adsorbent shows promising application in oil spill cleanup.

Study on the morphological regulation mechanism of hollow silica microsphere prepared via emulsion droplet template

The morphology regulation of hollow silica microspheres is significant for their properties and applications. In this paper, hollow silica microspheres were formed through the hydrolysis and condensation reaction of tetraethyl orthosilicate (TEOS) at the interface of the emulsion droplet templates composed of liquid paraffin and TEOS, followed by dissolving paraffin with ethanol. The effects of various factors including the emulsifier structure and content, TEOS content, catalyst type, and the ethanol content in the continuous water phase on the particle size, shell thickness and morphology of the prepared hollow silica microspheres were studied in detail. The results show that the diffusion and contact of TEOS and water molecules as well as the hydrolysis condensation reaction of TEOS at the oil-water interface are two critical processes for the synthesis and morphological regulation of hollow silica microspheres. Cationic emulsifier with a hydrophobic chain of appropriate length is the prerequisite for the successful synthesis of hollow silica microspheres. The ethanol content in water phase is the dominant factor to determine the average diameter of hollow microspheres, which can vary from 96 nm to 660 nm with the increase of the volume ratio of alcohol-water from 0 to 0.7. The silica wall thickness varies with the content and the hydrophobic chain length of the emulsifier, TEOS content, and the activity of the catalyst. The component of the soft template will affect the morphology of the silica wall. When the liquid paraffin is replaced by cyclohexane, hollow microspheres with fibrous mesoporous silica wall are fabricated. This work not only enriches the basic theory of interfacial polymerization in the emulsion system, but also provides ideas and methods for expanding the morphology and application of hollow silica microspheres.

Superhydrophobic starch-based adsorbent with honeycomb coral-like surface fabricated via facile immersion process for removing oil from water

The development of novel superhydrophobic adsorbents is highly demanded for tackling frequent oil spill accidents. Porous starch-based materials have been proven to possess good oil absorption performance, but their superhydrophobicity has not yet been reported, thus limiting their application in oil spill cleanup. Herein, a superhydrophobic starch-based adsorbent (MSC) was fabricated through the facile immersion process of starch cryogel (SC) into toluene solution of methyltrichlorosilane (MTS). Low-surface-energy and honeycomb coral-like micro/nanostructures, which contribute to high water contact angle (>151.0°) and low sliding angle (<15.0°), were provided simultaneously to SC by the hydrolysis-condensation reaction of MTS. MSC exhibited excellent water repellent, self-cleaning, and anti-fouling properties, as well as passable mechanical and chemical durability. The reasonable oil adsorption performance and selective wettability toward oil and water allowed this absorbent to be applied for heavy oil removal underwater and oil slick cleaning from the water surface. It is expected that the facile strategy provided by this work will accelerate the application of superhydrophobic starch-based materials in oil contamination removal and other industrial activities.

Synthesis and self-cleaning properties of superamphiphobic coatings based on burr-like copolymer particles

ABSTRACT Superhydrophobic and superoleophobic surfaces are widely used in many fields. Inspired by the structure of water strider legs, we proposed a simple method to construct a superamphiphobic surface based on burr-like KH-PS (copolymer of styrene and γ-Methacryloxypropyl trimethoxy silane) nanoparticles by soap-free emulsion polymerization and hydrolytic condensation reaction. In order to improve the film-forming properties and adhesion between coating and substrate, fluoromonomer-containing polysiloxane acrylate (PA) is designed and synthesized to bond burr-like nanoparticles. Then modify the fluorine-containing material on the surface of the burr-like particles to reduce the surface energy. The contact angles of the coating to water, diiodomethane, hexadecane, soybean oil, and rapeseed oil are 164.2° ± 1.5°, 155.3° ± 1.7°, 148.6° ± 1.9°, 152.7° ± 1.6°, and 153.5° ± 1.7°, respectively. The superamphiphobic coating exhibits excellent thermal stability, chemical stability, and self-cleaning performance. The microscopic roughness of coating constructed by organic polymer particles has broader application prospects on soft substrates such as fabrics.

Organic-Inorganic Hybrid Material Synthesis by on Line Coupling Twin Screw Extruder with a Microwave Oven

Abstract A new process for elaborating continuously organic-inorganic hybrid materials by reactive extrusion is presented. This synthesis consists in formulating a copolymer of ethylene and vinyl acetate (EVA)/tetrapropoxysilane (TPOS or Si(OC3H7)4)/catalyst blend by a corotating twin screw extruder followed by two successive reaction steps: on line microwave crosslinking reaction and hydrolysis-condensation reactions leading to a silica network cografted onto the organic matrix. Extrusion feed rate (Q), temperature, microwave oven power (P), and microwave curing time (tmw) were studied. Crosslinking density was evaluated before and after hydrolysis-condensation reactions and compared with the previous results obtained in static conditions. These materials tailored by an on line process present a permanent elasticity at high temperature (up to 200 °C) and a certain optical transparency. This new approach offers the possibility to synthesize massive samples based on organic-inorganic hybrid material.

Cationic polyelectrolyte-assisted synthesis of silica nanochains for enhancing mechanical properties of sodium alginate composite films

For the improvement of the transparency of silica nanomaterials and their dispersibility in polymer films, a series of silica nanochains were synthesized via a simple and cost-effective self-assembly method. Herein, silica oligomers were prepared through chemical hydrolysis-condensation reactions of tetramethyl orthosilicate; the growth of negative-charged silica oligomers in the confinement of positive-charged poly(dimethyldiallylammonium chloride) (PDDA) led to the formation of silica nanochains. By tuning the synthesis parameters (i.e., PDDA concentration, reaction temperatures, water:ethanol volume ratios, and ammonium water contents), it is possible to control the structure of silica nanochains and subsequently mechanical properties of sodium alginate (SA) composite films. Using optimal synthesis parameters, the obtained silica nanochains exhibited exceptional performances with high transparency, excellent hydrophilicity and good dispersibility, which surpassed silica nanospheres. Compared with pure SA film, the tensile strength and storage modulus in the glassy region of the SA composite film containing 0.5 wt% silica nanochains was improved by 93.0% and 824.7%, respectively. The work demonstrates the great promise of such silica nanochains toward practical application in optoelectronic thin-film materials.

Improve the mechanical durability of superhydrophobic/superamphiphobic coating through multiple cross-linked mesh structure

Superhydrophobic/superamphiphobic coatings have attracted extensive attention because of their unique liquid repellency, but their poor durability hinders their large-scale application in the market. This paper designs and synthesizes a mesh structure that uses covalent bonds to link the roughness-building nanoparticles, film-forming polymer, and the substrate together, which significantly improves the stability and durability of the coating. Firstly, the acrylate copolymer (FHA) containing silicon monomer and fluorine monomer was synthesized by free radical polymerization. Then FHA, SiO2/TiO2 nanoparticles, and self-made crosslinker (AG) were connected to form a meshwork structure by Si-O-Si bond through a hydrolysis condensation reaction. Finally, the curing agent (HDI) was added before dip-coating, and the coatings were firmly linked to the substrate through secondary cross-linking. The single-factor experiment showed that when silicon monomer was 12 wt%, fluorine monomer was 5 wt% and FHA content was 16 wt%, the coatings displayed the 5B adhesion. The contact angle (CA) to water, diiodomethane, soybean oil， rapeseed oil, hexadecane, kerosene, waste engine oil on the FAFH-SiO2 coating (consists of the mesh structure and SiO2 nanoparticles) were 158.7° ± 1.5°, 151.1° ± 1.6°, 150.1° ± 1.7°, 150.4° ± 1.5°, 141.1° ± 1.6°, 142.2° ± 1.9°, and 144.7° ± 1.8°, respectively. The coatings could maintain WCA (water contact angle) > 150° after immersion in HCl (PH = 1), toluene, ethanol, and acetone for 84 h. The sandpaper abrasion, water flow scouring, high-pressure steam cooking, machine washing, and environmental exposure tests proved that the coatings have excellent stability and durability. This method for enhancing the durability of the coatings is suitable for particles and substrates containing active hydrogen or hydroxyl groups, which has a wide range of application prospects.

Preparation and properties of benzocyclobutene based low-k linear polysiloxane

Linear BCB-containing polysiloxane with low k, low CTE, high T5 and high transparency was synthesized through Heck reaction and hydrolysis condensation reaction.

Water-stable halide perovskite nanocrystals in biological environment

Tetramethyl orthosilicate and triethoxyphenylsilane, which contains hydrophobic phenyl groups, were used as a silica (SiO2) source in a modified ligand-assisted reprecipitation synthesis approach for the fabrication of water-stable perovskite nanocrystals. Hydrolysis-condensation reaction of tetramethyl orthosilicate and triethoxyphenylsilane results in a formation of 3D siloxane network. Employing triethoxyphenylsilane in the synthesis enhances the hydrophobic properties of the SiO2 shell, which increases the stability of perovskites in aqueous medium. The stability of the CsPbBr3@SiO2 nanocrystals was estimated after 24 h of water exposure by the photoluminescence measurements at different time points. The synthesized CsPbBr3@SiO2 nanocrystals were visualized during in vitro experiments with murine melanoma B16-F10 cells. Hence, the potential of CsPbBr@SiO2 nanocrystals for bioimaging purposes was observed.

POSS modified NixOy-decorated TiO2 nanosheets: Nanocomposites for adsorption and photocatalysis

NixOy (NiO, Ni2O3) nanoparticles modifies titanium dioxide nanosheet (T) via one-step hydrothermal method, and then bis (vinyl)-hexa (trimethoxyethyl)-polysilsesquioxane (BH-POSS) is distributed on NixOy-T (NT) by utilizing hydrolysis condensation reaction procedure. Thus, BH-POSS/NixOy-T (PNT) is successfully obtained which exhibits boosted absorption ability and enhanced visible light photocatalytic efficiency. Above all, the maximum adsorptioncapacity(qm) of PNT is up to 848.458 mg/g forcrystalviolet (CV) within 5 min estimated by Langmuir adsorption model which is 18.7-fold larger as compared to T. Under visible light, the optimal PNT achieves the highest degradation rate constant value (Kapp) for rhodamine B (RhB) of 0.0150 min−1, which is 2.4-fold higher than that of NT. In addition, the present work may help us gain deeper insight into the synergistic effect between the BH-POSS that has larger absorption and NT heterojunction that accelerates electrons-holes separation and provide us with a new design route to make PNT considered as a promising material.

The Influence of HCl Concentration on the Rate of the Hydrolysis-Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under "Pseudo"-Equilibrium Conditions.

The rate of hydrolysis–condensation reaction of phenyltrichlorosilane in water-acetone solutions and the product yields were shown to significantly depend on the concentration of HCl (CHCl) in the solutions. The main product of the reaction was all-cis-(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane. This was different from the earlier published results of analogous reactions of m-tolylSiCl3, m-ClPhSiCl3, and α-naphtylSiCl, in which some products of other types were formed. For example, trans-1,1,3,3-tetrahydroxy-1,3-di-α-naphtyldisiloxane was obtained in the case of α-naphtylSiCl3. All-cis-(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane was treated in acetone with HCl to give the other three geometric isomers (cis-cis-trans-, cis-trans-, and all-trans-). The thermal self-condensation of these four isomers under “pseudo”-equilibrium conditions (under atmospheric pressure) was investigated in different solvents, in quartz or molybdenum glass flasks. The compositions of the products were monitored by APCI-MS and 29Si NMR spectroscopy. It was shown that all-cis- and cis-cis-trans-isomers in toluene or anisole mostly gave the cage-like Ph-T8,10,12,14 and uncompleted cage-like Ph-T10,12OSi(HO)Ph compounds. In contrast to these two isomers, the cis-trans–isomer in toluene mainly formed dimers with the loss of one or two molecules of water. However, in acetonitrile, significant amounts of Ph-T10,12 and Ph-T10,12OSi(HO)Ph species were formed along with the dimers. All-trans-isomer did not enter into the reaction at all.

An early detection of prostate cancer drug in water to prevent loss of biodiversity

Flutamide is a man-made non-steroidal anti-androgen drug that is extensively used for the prostate cancer therapy. Though the drug has a higher benefit ratio in treating cancer, it also exhibits certain lethal side effects to humans. It acts as an environmental pollutant instigating water pollution and aquatic organism damage by interfering in their reproductive cycle and its effect on aquatic life is a major concern. Hence, it is mandatory to detect the presence of this nitro-aromatic compound. For the effective determination of this analyte, gold modified Polyhedral Oligomeric Silsesquioxane (abbreviated as POSS-S-Au) based organic-inorganic hybrid material as chemical modifier has been used. This material synthesized via a hydrolysis-condensation reaction technique followed by a phase transfer method is utilized for the first time in the electrochemical determination of anti-cancer drug. The as-synthesized nanomaterial has been subjected to various Physio-chemical characterization and the Fourier Transform- Infrared Spectroscopy (FT-IR) spectra confirm the presence of -SH organic group and Si-O-Si stretch. X-ray Photoelectron Spectroscopy (XPS) spectra affirms the presence of silicon, oxygen, gold, and Sulphur owing to the introduction of gold through the thiolation of silicate core. The fabricated sensor showed excellent electro-catalytic activity for detecting flutamide with limit of detection (LOD) of 0.12 μM, and higher sensitivity of around 0.048 μA/μM.

High yield synthesis of hexitols and ethylene glycol through one-pot hydrolytic hydrogenation of cellulose

Catalytic valorization of biomass has gained a significant global attention in recent years. Cellulose is an interesting bio-renewable feedstock, which can be utilized to replace the fossil fuel derived chemicals to attain a sustainable bio-based economy. Our research shows a one-pot conversion of cellulose through hydrolytic hydrogenation using heteropolyacid (HPA)/zirconia and Ru/C catalyst. The developed catalytic system was found to be highly active towards selective production of hexitols and ethylene glycol. A significant improvement in the catalytic performance towards cellulose conversion was observed when the cellulose was pre-treated using ball-milling (900 rpm, 8 h), as the ball-milling significantly reduced the crystallinity index of cellulose, which decreased the recalcitrance of the cellulose structure. Almost complete conversion (100%) of cellulose was observed when the reaction was performed at 220 °C for 5 h giving hexitols and ethylene glycol yields of 26.2 and 40%, respectively. Based on a series of experiments, a possible reaction pathway was proposed which suggested heteropolyacid/zirconia catalyzed hydrolysis and retro-aldol condensation reactions, accompanying by hydrogenation with Ru/C. Interestingly, HPA immobilized on the composite catalyst shows enhanced stability and recyclability, demonstrating the utilization of a heterogeneous system for tandem conversions of biomass to renewable fuels and feedstocks.