Preparing flake nanocelluloses with hydrophobic surface from the spent liquor of cellulose nanocrystals

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In the present study, a special flake-like nanocellulose crystals (FCNCs) were self-assembled from the dissolved cellulose chains with low molecular weight via a "bottom-up" approach. The average diameters of FCNCs were 712 nm, with thickness in the range of 3 ~ 3.5 nm. They exhibited superior thermal stability relative to CNCs. XRD characterization revealed that the FCNCs with the cellulose type II structure possessed the hydrophobic (110) plane as the exposed surface which endowed the material with relatively hydrophobic property. Confirmed by the contact angle tests, the water contact angle value of FCNCs film was as high as 72.0°, almost twofold of that of CNCs film. Cellulose nanocrystals Acid hydrolysis Flaky morphology Waste liquor recycling Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Introduction Given the escalating scarcity of non-renewable resources and the accelerating environmental degradation, it is imperative to develop materials that are both renewable and biodegradable while exhibiting exceptional properties. Cellulose could be extracted from diverse sources (Fernandes et al. 2013 ; Moon et al. 2011 ), such as plants (George and Sabapathi 2015 ), bacteria (Rangaswamy et al. 2015 ), and algae (Mihranyan 2011 ) and is the most abundant natural polymer on Earth (Bochek 2003 ; Hinterstoisser and Salmén 2000 ). Its nanoscale derivate, namely, cellulose nanocrystals (CNCs), has been widely used in chemical, medical, food and textile fields due to its low cost, sustainability, biocompatibility, and biodegradability (He et al. 2021 ; Long et al. 2018 ; Wang et al. 2017 ). Except for the commonly seen rod-like CNCs and cellulose nanofibers (CNFs), cellulose nanomaterials with novel morphologies, such as spherical cellulose nanocrystals (SCNCs) (Tian et al. 2022 ), flaky cellulose nanocrystals (FCNCs) (Zhang et al. 2020 ), hollow cellulose spheres (Yan et al. 2018 ), etc. have been prepared in recent years. The SCNCs command much larger specific surface area (Yu et al. 2017 ), which may greatly enhance their water dispersibility and surface activity. Lu et al. reported that a kind of two-dimensional nanocellulose with cellulose I structure could be used for polymer reinforcement (Lu et al. 2020 ). Manipulation of cellulose molecules at the nanoscale level to obtain nanocellulose with various morphologies and exceptional properties has emerged as a prominent research focus in the field of cellulose (Habibi et al. 2010 ). Cellulose nanomaterials are often prepared via mechanical approach (e.g. ball milling and high-pressure homogenization)(Wang et al. 2019 ), chemical approaches (e.g. strong acid hydrolysis (Mandal and Chakrabarty 2011 ; Shang et al. 2019 ), TEMPO treatment (Liu et al. 2020 )), or enzyme treatment (Tao et al. 2019 ). Among them, acid hydrolysis is the most common method. Using sulfuric acid as the hydrolysis solution, the obtained nanocellulose suspension exhibited enhanced stability owing to the incorporation of negatively charged sulphate groups onto the surface of nanocelluloses (Beck-Candanedo et al. 2005 ). Hydrochloric acid hydrolysis of cellulose exhibits superior catalytic efficiency, milder hydrolysis conditions (Kasiri and Fathi 2018 ). In most cases, mixed acid hydrolysis with sulfuric and hydrochloric acids is used, considering the advantages of both methods. In general, the yield of nanocellulose prepared by acid hydrolysis falls into the range of 15% ~ 70%, depending on the starting materials and reaction conditions. It means that at least 30% of the cellulose with low molecular weight is discarded as part of the spent liquor (Niu et al. 2017 ; Noremylia et al. 2022 ; Xie et al. 2018 ). For commercial preparation of CNCs, it is of great value to isolate such dissolved carbohydrates and reuse them to synthesize valuable products. Hu et al. (Hu et al. 2014 ) reported a method for synthesizing highly crystalline type II SCNCs by utilizing the waste liquor from the preparation of CNCs. Similarly, SCNCs could be obtained from the waste liquor by H 2 SO 4 /HCl mixed acid hydrolysis (Wang et al. 2007 ). Nevertheless, the spent carbohydrates in the waste liquor did not receive the attention it deserved. In the present study, we presented a straightforward methodology for synthesis of nanocelluloses with diverse morphologies, i.e. flaky and spherical cellulose nanocrystals from the spend liquor of CNCs. Specifically, the prepared FCNCs with exposed (110) surface showed relatively hydrophobic characteristic. The unique structure and surface property of the FCNCs could open up more possibilities for nano-cellulose applications. The reuse of spent liquor provides a route towards green chemistry. Experimental Materials Microcrystalline cellulose (diameter, D = 25µm), sodium hydroxide (NaOH, AR), dimethyl sulfoxide (DMSO, AR), sulfuric acid (H 2 SO 4 , 96%-98%) and hydrochloric acid (HCl, 36–38%) were purchased from Sinopharm Chemical Reagent Co., Ltd. Water used in all experiments was deionized water (DI H 2 O). Preparation of cellulose nanocrystals The MCC was pre-dried in a vacuum oven at 50°C for 2 hours. NaOH of 5 mol/L and DMSO were used as prior treatment reagents. 30 g MCC was first reacted with 250 ml NaOH at 80°C for 3 h, and the cellulose was filtered, washed with DI H 2 O until the neutral pH and dried in a freeze-dryer. Then the cellulose treated with 250 ml DMSO at 80°C for another 3 h, and the cellulose was centrifuged, washed and dried in the freeze-dryer, then obtained pre-treated MCC. Figure 1 illustrates the steps involved in the extraction of three different forms of nanocelluloses from MCC. The pre-treated MCC was hydrolyzed by a mixed acid solution for 10 h at 75°C. The H 2 SO 4 , HCl and DI H 2 O were mixed at a ratio of 3:1:6 (v/v) to obtain the mixed acid solution, and the ratio of the cellulose to mixed acid solution was 20 mg/ml. The suspension obtained from the reaction was subjected to centrifugation at 8000 rpm for 8 minutes in order to separate the precipitate and supernatant (waste liquor, saved for later use). Subsequently, the precipitate was dispersed in DI H 2 O and subjected to centrifugation at 8000 rpm for 8 minutes. The resulting supernatant was decanted, and this process was repeated twice. Finally, the precipitate was transferred inside dialysis membrane tubes (8000–12000 Da molecular weight cut off), dialyzed against slow running DI H 2 O for 4 days, and subsequently dried in the freeze-dryer for three days to obtain the CNCs. The waste liquor obtained during the preparation of CNCs was filtered three times. It was then transferred into the dialysis membranes and dialyzed against slow running DI H 2 O for 7 days. During dialysis the crystals settled down at the bottom of the membrane, leaving a clear top layer. The precipitate and clear top layer were separated by filtration. These two parts were freeze-dried to obtain FCNCs and SCNCs, respectively. Characterization Scanning electron microscope (SEM) The microstructures and the surface morphologies of samples were examined by a scanning electron microscope (SUPRA 35) after gold coating (Cressingon208HR). Transmission electron microscopy (TEM) The three different morphologies of nanocelluloses were re-dispersed into DI H 2 O. The suspensions of CNCs, FCNCs, and SCNCs were dropped on the carbon-coated electron microscopy grids, air-died. The sample grids were observed at 200 kV using a FEI Tecnai F20. Atomic Force Microscopy (AFM) A very dilute suspension (0.01–0.02 wt.%) was drop cast on a glass slide. The slide was dried overnight under ambient conditions, and examined using a Bruker Dimension Icon AFM. X-ray diffractometry (XRD) The crystal structures of CNCs, FCNCs, and SCNCs was characterized by XRD (Bruker D8 Advance) at a scanning speed of 4°/min in the angular of 5–90° with Cu Kα. Fourier transform infrared (FTIR) The chemical compositions were measured at 2 cm − 1 resolution by a FT-IR, Bruker VERTEX 70v spectrum scanner. X-ray photoelectron spectroscopy (XPS) The chemical compositions of nanocelluloses were subsequently characterized using XPS (Kratos Axis Ultra (DLD), Al Kα radiation source). Thermalgravimetric analysis (TGA) The thermal decomposition behavior of MCC and nanocelluloses was studies by TGA Q500 V20.13 Build 39. Contact angle tests The water contact angles of CNCs, FCNCs, and SCNCs were measured by a contact angle analyzer (JC2000D1) at room temperature in air. Results and Discussion Structures of CNCs and FCNCs The obtained cellulose nanomaterials were characterized by microscopic techniques. Resembling to most of the CNCs prepared by acid hydrolysis, the obtained CNCs in our experiments were rod-like nanofibers (Fig. 2 (a) and (b)). According to the TEM images, the mean diameter and length of the short fibers were measured to be about 11 nm and 142 nm, respectively. The FCNCs were obtained from the spent liquor. Figure 2 (d) and (e) display the SEM and TEM micrographs of FCNCs. The special cellulose products also showed homogeneous appearance. The flake-like morphology of FCNCs was obviously distinct with the commonly seen CNCs and CNFs. Inset in Fig. 2 (e) was a zoom-in image of the corner of a nanoflake, which clearly indicated that some of the flaky celluloses were composed of stacked thin layers. The size of the flakes was statistically measured and given as a histogram in Fig. 2 (f). Most of the cellulose flakes were in the range of 550–850 nm in size. As described in Section 2.2, SCNCs were obtained by freeze-drying of the clear top layer in the dialysis tubing. Microscopy analysis was carried out on the product as well. The results are shown in Fig. S1 . The diameter of the SCNCs was about 60 nm in average. Since SCNCs had been prepared from the spend liquor in a previous work, the FCNCs were mainly focused in the present study. The thickness of the FCNCs was determined by AFM. As shown in Fig. 3 , the cellulose nano-flakes were well dispersive. Directly measurement indicated the flakes were about 3 ~ 3.5 nm in thickness. Compared with the width scale (~ 700 nm), the flake could be deemed as a two-dimensional material. XRD was carried out to study the crystallographic structures of the MCC and nanocelluloses (Fig. 4 ). Three cellulose Ⅰ characteristic peaks at 2θ = 14.8°, 16.4°, and 22.6° (Wada et al. 2004 ) are shown in the profile of the raw material MCC. The diffraction peaks can be indexed by Miller indices of (1 \(\stackrel{-}{1}\) 0), (110) and (200) planes belonged to a one-chain triclinic unit cell (Cellulose I structure). The nanocelluloses exhibited three distinct peaks at 12.1°, 20.0°, and 21.7°, corresponding to the (1 \(\stackrel{-}{1}\) 0), (110), and (020) crystallographic planes of Cellulose II (Yan et al. 2015 ), respectively. However, carefully inspection on the diffraction patterns of these nanocelluloses indicated that the (110) plane of FCNCs showed relatively strong diffraction, compared to the peak of CNCs. The results suggested that the self-assembled FCNCs had preferred crystalline orientation. In combination with the microscopy observations, it was clear that the cellulose nano-flakes should have exposed (110) surfaces. On the other hand, the (110) diffraction peak exhibited obvious broadening, suggesting the length scale of the material along this direction was quite small, which also confirmed the two-dimensional characteristic of the material. The FTIR spectra of MCC and nanocelluloses are shown in Fig. 5 . Both MCC and nanocelluloses exhibited C-H stretching vibrations peaks at 2900 cm − 1 . The absorption peak of the O-H stretching vibration of microcrystalline cellulose was at 3346 cm − 1 . In contrast, the FTIR spectra of CNCs and FCNCs showed an absorption peak of the O-H stretching vibration between 3425–3444 cm − 1 , indicating the hydrogen bonding stretching of type II cellulose (Zhang et al. 2009 ). The shift reflected the weaker inter- and intrachain hydrogen bonds of the nanocelluloses. Furthermore, for microcrystalline cellulose, the 1430 cm − 1 band was relatively strong, whereas it weakened and shifted to 1416 cm − 1 for nanocelluloses. This suggested that the conformation of the primary alcohol hydroxyl CH 2 OH at the C6 position in cellulose changes from trans-gauche (tg) to gauche-trans (gt), indicating the transition from cellulose type I to type II. The above characteristics in FTIR spectra all confirmed the crystalline structures of MCC, CNCs and FCNCs determined by XRD analysis. As shown in Fig. 6 , XPS was used to further investigate chemical compositions of the surfaces of CNCs, FCNCs, and SCNCs. All samples were primarily composed of carbon and oxygen atoms. The XPS C 1s spectrums of the three nanocelluloses all exhibited two distinct peaks with binding energies of 286.6, and 287.9-288.3 eV, corresponding to cellulose C-O, and O-C-O, respectively. Besides cellulose, C 1s also showed a peak with binding energies of 284.8 eV, corresponding to aliphatic carbons C-C/C-H(Yan et al. 2015 ). However, the O/C ratios varied from sample to sample. Compared with CNCs and SCNCs, the O/C ratio of FCNCs was significantly reduced. This observation might indicate a less presence of adsorbed water on the surface of FCNCs (Koljonen et al. 2003 ). Thermal properties of CNCs and FCNCs The thermos gravimetric and derivative thermos gravimetric curves of microcrystalline cellulose and nanocelluloses are shown in Fig. 7 . These cellulose nano-materials exhibited significantly different thermal characteristics relative to the MCC. Decomposition of the MCC initiated at the temperature of 257 ℃. The maximum weight loss appeared at 327 ℃. The onset decomposition temperatures and maximum weight loss temperatures of CNCs and FCNCs were lower than those of MCC. Specifically, CNCs had an onset decomposition temperature of 124°C and a maximum weight loss temperature of 180°C. The two characteristic temperatures for FCNCs were 167°C and 298°C, respectively. On the other hand, the nanocelluloses showed more gradual thermal transition. MCC lost nearly 82% of its mass between 300–400°C, leaving only 7.4% ash at 600°C. In contrast, FCNCs lost 53% of their mass in the range of 167–300°C, followed by approximately 24% of their mass between 300–600°C, leaving 15% of their mass behind. CNCs lost 36% of their mass in the initial decomposition temperature range up to 300°C, and 30% of their mass between 300–600°C. Meanwhile, CNCs retained more residue, close to about 30%. These major differences in thermal behaviors between the CNCs and the FCNCs might be attributed to variations in surface area, morphology, and particle size. The high surface area of nanocelluloses is a significant factor in reducing their thermal stability, as a consequence of the increased surface area exposed to heat (Lu and Hsieh 2010 ). Furthermore, it was reported that the thermal degradation of one nanofiber could lead to degradation in neighboring nanofibers (Quiévy et al. 2010 ). It could be observed from SEM and TEM that, CNCs were smaller than FCNCs in size and had more contact with each other, which resulted in enhanced thermal conductivity. Moreover, due to the large-diameter flaky structure of FCNCs, fewer readily decomposable free end chains were formed on the surface of FCNCs relative to that of CNCs (Zhao et al. 2019 ). Consequently, FCNCs began to decompose at relatively high temperatures. Compared to CNCs, FCNCs were more thermally stable but had a lower carbon residual rate. The results suggested that FCNCs possess relatively better thermal stability. Additionally, both CNCs and FCNCs exhibited lower weight loss, which could potentially enhance the amorphous carbon yield. Surface property of FCNCs The above profile and structural features of nanocelluloses revealed that FCNCs had (110) exposed surfaces. The formation mechanism is analyzed as shown in Fig. 8 . Cellulose is composed of alternating crystalline and amorphous regions. During hydrolysis, amorphous regions were preferentially hydrolyzed, whereas the crystalline domains were more predictable to be preserved to form CNCs (Habibi et al. 2010 ). Nevertheless, hydrolysis produced small-sized cellulose fragments that were dispersed in acid solutions due to the repulsive force of their surface negative charges. During dialysis, as the acidity of the solution diminishing, the H-bonding and van der Waals forces between the cellulose molecules gradually overcame the repulsive forces of the negative charges on their surfaces, resulting in aggregation and stacking (Lu and Hsieh 2010 ). It has been demonstrated that cellulose type II structure is the most thermodynamic stability of molecular chains stacking. The H-bonding between the molecular chains precisely aligned the cellulose molecular chains along their crystallographic [1 \(\stackrel{-}{1}\) 0] directions, resulting in a two-dimensional structure with (110) surface exposed. Then, the molecules between the (110) surfaces were stacked by van der Waals forces to form two-dimensional cellulose nanocrystals with a certain thickness (3 ~ 3.5 nm in the present case). According to the atomic projection in the middle part in Fig. 8 , each dehydrated glucose unit of the cellulose adopts a 1 C 4 chair conformation, with the all alcohol substituents in the ring plane, while the hydrogen atom in the vertical position. Therefore, in a manner analogous to the (200) surface of cellulose type I β structure (Mazeau and Rivet 2008 ; Zhang et al. 2020 ), the (110) surface of cellulose type II structure exhibited a relatively hydrophobic characteristic, with the hydrophobic C-H moieties exposed to the surrounding medium. To confirm this deduction, contanct angle tests were used to evaluated the hydrophobicity of the FCNCs (Fig. 9 ). It was observed that the water contact angle on FCNC film was considerably larger than that on CNCs. The contact angle value for CNCs was found to be 43.5°, while that for FCNCs reached 72.0°. This finding indicated that FCNCs possess apparently hydrophobic surface. The results of the contact angle experiments reversely verified that the (110) surface was actually the main exposed surface of FCNCs. Conclusions The flaky nanocelluloses were isolated using the waste liquor of CNCs prepared by acid hydrolysis. The FCNCs exhibit Cellulose type II crystalline structure with exposed (110) surface. The average diameters of FCNCs were 712 nm, with height between 3 ~ 3.5 nm. FCNCs were formed through self-assembly of low molecular weight cellulose chains via hydrogen-bonding between the molecular chains. Exposed (110) surfaces endow the new type of nanocellulose with hydrophobic property which was confirmed by contact angle tests. The water contact angle value was measured to be as high as 72.0°. Successful extraction of flaky nanocelluloses from the cellulose hydrolysis waste liquor not only reduces waste in production processes of cellulose nanocrystals, but also provide more possibilities for cellulose application owing to the unique structure and surface property. Declarations Acknowledgements This work is financially supported by the research foundation of SYNL (L2019F15). W.Z. and J.W. acknowledge the support by Liaoning Provincial Science and Technology Plan Project (No.2023-MS-067). Author contributions All authors contributed to the study conception and design. J.L., X.J., and G.G. conducted the experiments and wrote the main manuscript text. W.Z. and J.W. analyzed the data and modified the grammar. Y.Z. and D.L. instructed the experiments and revised the manuscript. Funding This work is supported by the research foundation of SYNL (L2019F15) and Liaoning Provincial Science and Technology Plan Project (No.2023-MS-067). 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ACS Sustainable Chemistry & Engineering 8:9277–9290. https://doi.org/10.1021/acssuschemeng.0c00464 Zhao GM, Du J, Chen WM, Pan MZ, Chen DY (2019) Preparation and thermostability of cellulose nanocrystals and nanofibrils from two sources of biomass: rice straw and poplar wood. Cellulose 26:8625–8643. https://doi.org/10.1007/s10570-019-02683-8 Additional Declarations No competing interests reported. Supplementary Files SupportingInformation.docx Cite Share Download PDF Status: Published Journal Publication published 03 Feb, 2025 Read the published version in Cellulose → Version 1 posted Editorial decision: Revision requested 04 Jul, 2024 Editor assigned by journal 04 Jul, 2024 Submission checks completed at journal 04 Jul, 2024 First submitted to journal 27 Jun, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4649995","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":322794360,"identity":"9f9111e3-330b-49ee-8f2c-6d448e1bfc17","order_by":0,"name":"Jiebai Li","email":"","orcid":"","institution":"Institute of Metals Research","correspondingAuthor":false,"prefix":"","firstName":"Jiebai","middleName":"","lastName":"Li","suffix":""},{"id":322794362,"identity":"31ff198e-8126-4754-b7e4-9a9e787b78a1","order_by":1,"name":"Dongyan Liu","email":"","orcid":"","institution":"Institute of Metals Research","correspondingAuthor":false,"prefix":"","firstName":"Dongyan","middleName":"","lastName":"Liu","suffix":""},{"id":322794364,"identity":"dee70a80-8f45-467b-aecb-fd11b8565031","order_by":2,"name":"Xilin Jia","email":"","orcid":"","institution":"Institute of Metals Research","correspondingAuthor":false,"prefix":"","firstName":"Xilin","middleName":"","lastName":"Jia","suffix":""},{"id":322794365,"identity":"adee5d97-916e-441f-9dcc-a1dc2abca99d","order_by":3,"name":"Guangguang Guan","email":"","orcid":"","institution":"Institute of Metals Research","correspondingAuthor":false,"prefix":"","firstName":"Guangguang","middleName":"","lastName":"Guan","suffix":""},{"id":322794368,"identity":"388d60f0-b4a2-4c00-8598-c77a736af662","order_by":4,"name":"Wenbo Zhang","email":"","orcid":"","institution":"Yingkou Science and Technology Innovation Service Center","correspondingAuthor":false,"prefix":"","firstName":"Wenbo","middleName":"","lastName":"Zhang","suffix":""},{"id":322794370,"identity":"4f83d7c4-2a76-4002-8242-f83116af58c9","order_by":5,"name":"Jingyuan Wei","email":"","orcid":"","institution":"Liaoning Academy of Analytical Sciences","correspondingAuthor":false,"prefix":"","firstName":"Jingyuan","middleName":"","lastName":"Wei","suffix":""},{"id":322794371,"identity":"82f487aa-d5e4-4372-8be0-c84c16111e74","order_by":6,"name":"Yangtao Zhou","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAArUlEQVRIiWNgGAWjYHACNiC24SFJA0hLGulaDpOgw+B++7MHH9vOy+jOPsD44QeDXR5hLccY0g1ntt3mMTuXwCzZw5BcTIyWY9K8IC1nGBikGRgOJDYQ1sLYBtRyDqSF+TeRWpjZgFoOgLSwEWeL5LE0NskZ55KBWhjbLHsMkglr4Tt8/JnEhzI7e7MzzIdv/KiwI6xF4QCcyQhUbEBIPRDIEzR0FIyCUTAKRgEAWcQ2ssIfyO8AAAAASUVORK5CYII=","orcid":"","institution":"Institute of Metals Research","correspondingAuthor":true,"prefix":"","firstName":"Yangtao","middleName":"","lastName":"Zhou","suffix":""}],"badges":[],"createdAt":"2024-06-27 16:16:52","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4649995/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4649995/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10570-025-06388-z","type":"published","date":"2025-02-03T15:58:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":61344628,"identity":"2f9061da-0a9f-439a-8472-01ce6d29a25e","added_by":"auto","created_at":"2024-07-29 17:42:31","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":134706,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of cellulose nanocrystals extraction from microcrystalline cellulose\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/cae3cc2a944ab5bc3df0ba03.jpeg"},{"id":61344957,"identity":"37de88c3-2cb1-449a-b9e9-0f9f7b644921","added_by":"auto","created_at":"2024-07-29 17:50:31","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":363638,"visible":true,"origin":"","legend":"\u003cp\u003e(a, b) SEM image and TEM image of CNCs. (c) Sizes distribution diagrams of the obtained CNCs. (d, e) SEM and TEM images of FCNCs. (f) Sizes distribution of FCNCs\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/313daea940df89fdc94e98e6.jpeg"},{"id":61344956,"identity":"2562913a-136f-4284-9748-c1d0274e8fc4","added_by":"auto","created_at":"2024-07-29 17:50:31","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":119201,"visible":true,"origin":"","legend":"\u003cp\u003e(a) AFM image of the FCNCs. (b) cross-sectional profile of typical FCNCs as denoted in (a). The thickness of the FCNC is about 3 nm\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/f75fb4af338e4f957b5d6a46.jpeg"},{"id":61344636,"identity":"afd7bbad-6d77-4b9b-b609-5a1c0e833276","added_by":"auto","created_at":"2024-07-29 17:42:32","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":106018,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray diffraction profiles of MCC, CNCs and FCNCs. The prepared CNCs and FCNCs all have the Cellulose II structure\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/b488f6ccf4b319c4868c17d6.jpeg"},{"id":61344630,"identity":"24b2cd17-b475-4291-af44-1f20cf82ee84","added_by":"auto","created_at":"2024-07-29 17:42:31","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":118990,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra for MCC and nanocelluloses\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/407cd772828cd46fb11ba986.jpeg"},{"id":61344626,"identity":"08d3f9a1-32c2-4513-a5dd-6e7f918b5cbb","added_by":"auto","created_at":"2024-07-29 17:42:31","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":187297,"visible":true,"origin":"","legend":"\u003cp\u003eXPS survey spectrum of nanocelluloses (a); and high resolutions C 1s spectra of (b) CNCs; (c) FCNCs\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/17281cc6e79e83656ad91530.jpeg"},{"id":61344958,"identity":"0dde571b-18ec-4556-9484-bc434927e8d3","added_by":"auto","created_at":"2024-07-29 17:50:31","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":137820,"visible":true,"origin":"","legend":"\u003cp\u003e(a) TGA and (b) DTGA for MCC and nanocelluloses\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/9a79aff9f43d5124c968cc81.jpeg"},{"id":61344632,"identity":"071e101c-1190-4e7f-af22-8dd722300d51","added_by":"auto","created_at":"2024-07-29 17:42:31","extension":"jpeg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":91610,"visible":true,"origin":"","legend":"\u003cp\u003ePossible scheme of FCNCs formation from spent liquor\u003c/p\u003e","description":"","filename":"floatimage8.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/bb1736fdaf197521f1190cdf.jpeg"},{"id":61344635,"identity":"88a28630-c3bd-439f-a364-b5af4551b4dc","added_by":"auto","created_at":"2024-07-29 17:42:32","extension":"jpeg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":32857,"visible":true,"origin":"","legend":"\u003cp\u003eContact angles of CNCs and FCNCs\u003c/p\u003e","description":"","filename":"floatimage9.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/43546c6ff57232c2fbfdef0f.jpeg"},{"id":75930502,"identity":"eed2217e-c8e5-4f4c-97d4-aedb541f3720","added_by":"auto","created_at":"2025-02-10 16:12:32","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1948270,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/529b5830-0112-4ea7-8509-fb530ee10a0a.pdf"},{"id":61344633,"identity":"4dda82aa-2a17-40b7-9411-3676bc891f92","added_by":"auto","created_at":"2024-07-29 17:42:31","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":502890,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4649995/v1/4fea2ea158c2674fd11290c4.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Preparing flake nanocelluloses with hydrophobic surface from the spent liquor of cellulose nanocrystals","fulltext":[{"header":"Introduction","content":"\u003cp\u003eGiven the escalating scarcity of non-renewable resources and the accelerating environmental degradation, it is imperative to develop materials that are both renewable and biodegradable while exhibiting exceptional properties. Cellulose could be extracted from diverse sources (Fernandes et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Moon et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2011\u003c/span\u003e), such as plants (George and Sabapathi \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), bacteria (Rangaswamy et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), and algae (Mihranyan \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2011\u003c/span\u003e) and is the most abundant natural polymer on Earth (Bochek \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2003\u003c/span\u003e; Hinterstoisser and Salm\u0026eacute;n \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2000\u003c/span\u003e). Its nanoscale derivate, namely, cellulose nanocrystals (CNCs), has been widely used in chemical, medical, food and textile fields due to its low cost, sustainability, biocompatibility, and biodegradability (He et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Long et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2017\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eExcept for the commonly seen rod-like CNCs and cellulose nanofibers (CNFs), cellulose nanomaterials with novel morphologies, such as spherical cellulose nanocrystals (SCNCs) (Tian et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), flaky cellulose nanocrystals (FCNCs) (Zhang et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), hollow cellulose spheres (Yan et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2018\u003c/span\u003e), etc. have been prepared in recent years. The SCNCs command much larger specific surface area (Yu et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), which may greatly enhance their water dispersibility and surface activity. Lu et al. reported that a kind of two-dimensional nanocellulose with cellulose I structure could be used for polymer reinforcement (Lu et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Manipulation of cellulose molecules at the nanoscale level to obtain nanocellulose with various morphologies and exceptional properties has emerged as a prominent research focus in the field of cellulose (Habibi et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eCellulose nanomaterials are often prepared via mechanical approach (e.g. ball milling and high-pressure homogenization)(Wang et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), chemical approaches (e.g. strong acid hydrolysis (Mandal and Chakrabarty \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Shang et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), TEMPO treatment (Liu et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2020\u003c/span\u003e)), or enzyme treatment (Tao et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Among them, acid hydrolysis is the most common method. Using sulfuric acid as the hydrolysis solution, the obtained nanocellulose suspension exhibited enhanced stability owing to the incorporation of negatively charged sulphate groups onto the surface of nanocelluloses (Beck-Candanedo et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2005\u003c/span\u003e). Hydrochloric acid hydrolysis of cellulose exhibits superior catalytic efficiency, milder hydrolysis conditions (Kasiri and Fathi \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). In most cases, mixed acid hydrolysis with sulfuric and hydrochloric acids is used, considering the advantages of both methods. In general, the yield of nanocellulose prepared by acid hydrolysis falls into the range of 15% ~ 70%, depending on the starting materials and reaction conditions. It means that at least 30% of the cellulose with low molecular weight is discarded as part of the spent liquor (Niu et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Noremylia et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Xie et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). For commercial preparation of CNCs, it is of great value to isolate such dissolved carbohydrates and reuse them to synthesize valuable products. Hu et al. (Hu et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2014\u003c/span\u003e) reported a method for synthesizing highly crystalline type II SCNCs by utilizing the waste liquor from the preparation of CNCs. Similarly, SCNCs could be obtained from the waste liquor by H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e/HCl mixed acid hydrolysis (Wang et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2007\u003c/span\u003e). Nevertheless, the spent carbohydrates in the waste liquor did not receive the attention it deserved.\u003c/p\u003e \u003cp\u003eIn the present study, we presented a straightforward methodology for synthesis of nanocelluloses with diverse morphologies, i.e. flaky and spherical cellulose nanocrystals from the spend liquor of CNCs. Specifically, the prepared FCNCs with exposed (110) surface showed relatively hydrophobic characteristic. The unique structure and surface property of the FCNCs could open up more possibilities for nano-cellulose applications. The reuse of spent liquor provides a route towards green chemistry.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials\u003c/h2\u003e \u003cp\u003eMicrocrystalline cellulose (diameter, D\u0026thinsp;=\u0026thinsp;25\u0026micro;m), sodium hydroxide (NaOH, AR), dimethyl sulfoxide (DMSO, AR), sulfuric acid (H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e, 96%-98%) and hydrochloric acid (HCl, 36\u0026ndash;38%) were purchased from Sinopharm Chemical Reagent Co., Ltd. Water used in all experiments was deionized water (DI H\u003csub\u003e2\u003c/sub\u003eO).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003ePreparation of cellulose nanocrystals\u003c/h2\u003e \u003cp\u003eThe MCC was pre-dried in a vacuum oven at 50\u0026deg;C for 2 hours. NaOH of 5 mol/L and DMSO were used as prior treatment reagents. 30 g MCC was first reacted with 250 ml NaOH at 80\u0026deg;C for 3 h, and the cellulose was filtered, washed with DI H\u003csub\u003e2\u003c/sub\u003eO until the neutral pH and dried in a freeze-dryer. Then the cellulose treated with 250 ml DMSO at 80\u0026deg;C for another 3 h, and the cellulose was centrifuged, washed and dried in the freeze-dryer, then obtained pre-treated MCC.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e illustrates the steps involved in the extraction of three different forms of nanocelluloses from MCC. The pre-treated MCC was hydrolyzed by a mixed acid solution for 10 h at 75\u0026deg;C. The H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e, HCl and DI H\u003csub\u003e2\u003c/sub\u003eO were mixed at a ratio of 3:1:6 (v/v) to obtain the mixed acid solution, and the ratio of the cellulose to mixed acid solution was 20 mg/ml. The suspension obtained from the reaction was subjected to centrifugation at 8000 rpm for 8 minutes in order to separate the precipitate and supernatant (waste liquor, saved for later use). Subsequently, the precipitate was dispersed in DI H\u003csub\u003e2\u003c/sub\u003eO and subjected to centrifugation at 8000 rpm for 8 minutes. The resulting supernatant was decanted, and this process was repeated twice. Finally, the precipitate was transferred inside dialysis membrane tubes (8000\u0026ndash;12000 Da molecular weight cut off), dialyzed against slow running DI H\u003csub\u003e2\u003c/sub\u003eO for 4 days, and subsequently dried in the freeze-dryer for three days to obtain the CNCs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe waste liquor obtained during the preparation of CNCs was filtered three times. It was then transferred into the dialysis membranes and dialyzed against slow running DI H\u003csub\u003e2\u003c/sub\u003eO for 7 days. During dialysis the crystals settled down at the bottom of the membrane, leaving a clear top layer. The precipitate and clear top layer were separated by filtration. These two parts were freeze-dried to obtain FCNCs and SCNCs, respectively.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eCharacterization\u003c/h2\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003eScanning electron microscope (SEM)\u003c/h2\u003e \u003cp\u003eThe microstructures and the surface morphologies of samples were examined by a scanning electron microscope (SUPRA 35) after gold coating (Cressingon208HR).\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003eTransmission electron microscopy (TEM)\u003c/h2\u003e \u003cp\u003eThe three different morphologies of nanocelluloses were re-dispersed into DI H\u003csub\u003e2\u003c/sub\u003eO. The suspensions of CNCs, FCNCs, and SCNCs were dropped on the carbon-coated electron microscopy grids, air-died. The sample grids were observed at 200 kV using a FEI Tecnai F20.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eAtomic Force Microscopy (AFM)\u003c/h2\u003e \u003cp\u003eA very dilute suspension (0.01\u0026ndash;0.02 wt.%) was drop cast on a glass slide. The slide was dried overnight under ambient conditions, and examined using a Bruker Dimension Icon AFM.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003eX-ray diffractometry (XRD)\u003c/h2\u003e \u003cp\u003eThe crystal structures of CNCs, FCNCs, and SCNCs was characterized by XRD (Bruker D8 Advance) at a scanning speed of 4\u0026deg;/min in the angular of 5\u0026ndash;90\u0026deg; with Cu Kα.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eFourier transform infrared (FTIR)\u003c/h2\u003e \u003cp\u003eThe chemical compositions were measured at 2 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e resolution by a FT-IR, Bruker VERTEX 70v spectrum scanner.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eX-ray photoelectron spectroscopy (XPS)\u003c/h2\u003e \u003cp\u003eThe chemical compositions of nanocelluloses were subsequently characterized using XPS (Kratos Axis Ultra (DLD), Al Kα radiation source).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eThermalgravimetric analysis (TGA)\u003c/h2\u003e \u003cp\u003eThe thermal decomposition behavior of MCC and nanocelluloses was studies by TGA Q500 V20.13 Build 39.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003eContact angle tests\u003c/h2\u003e \u003cp\u003eThe water contact angles of CNCs, FCNCs, and SCNCs were measured by a contact angle analyzer (JC2000D1) at room temperature in air.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and Discussion","content":"\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003eStructures of CNCs and FCNCs\u003c/h2\u003e \u003cp\u003eThe obtained cellulose nanomaterials were characterized by microscopic techniques. Resembling to most of the CNCs prepared by acid hydrolysis, the obtained CNCs in our experiments were rod-like nanofibers (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a) and (b)). According to the TEM images, the mean diameter and length of the short fibers were measured to be about 11 nm and 142 nm, respectively. The FCNCs were obtained from the spent liquor. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(d) and (e) display the SEM and TEM micrographs of FCNCs. The special cellulose products also showed homogeneous appearance. The flake-like morphology of FCNCs was obviously distinct with the commonly seen CNCs and CNFs. Inset in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(e) was a zoom-in image of the corner of a nanoflake, which clearly indicated that some of the flaky celluloses were composed of stacked thin layers. The size of the flakes was statistically measured and given as a histogram in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(f). Most of the cellulose flakes were in the range of 550\u0026ndash;850 nm in size. As described in Section 2.2, SCNCs were obtained by freeze-drying of the clear top layer in the dialysis tubing. Microscopy analysis was carried out on the product as well. The results are shown in Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. The diameter of the SCNCs was about 60 nm in average. Since SCNCs had been prepared from the spend liquor in a previous work, the FCNCs were mainly focused in the present study.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe thickness of the FCNCs was determined by AFM. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, the cellulose nano-flakes were well dispersive. Directly measurement indicated the flakes were about 3\u0026thinsp;~\u0026thinsp;3.5 nm in thickness. Compared with the width scale (~\u0026thinsp;700 nm), the flake could be deemed as a two-dimensional material.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eXRD was carried out to study the crystallographic structures of the MCC and nanocelluloses (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). Three cellulose Ⅰ characteristic peaks at 2θ\u0026thinsp;=\u0026thinsp;14.8\u0026deg;, 16.4\u0026deg;, and 22.6\u0026deg; (Wada et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2004\u003c/span\u003e) are shown in the profile of the raw material MCC. The diffraction peaks can be indexed by Miller indices of (1\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\stackrel{-}{1}\\)\u003c/span\u003e\u003c/span\u003e0), (110) and (200) planes belonged to a one-chain triclinic unit cell (Cellulose I structure). The nanocelluloses exhibited three distinct peaks at 12.1\u0026deg;, 20.0\u0026deg;, and 21.7\u0026deg;, corresponding to the (1\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\stackrel{-}{1}\\)\u003c/span\u003e\u003c/span\u003e0), (110), and (020) crystallographic planes of Cellulose II (Yan et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), respectively. However, carefully inspection on the diffraction patterns of these nanocelluloses indicated that the (110) plane of FCNCs showed relatively strong diffraction, compared to the peak of CNCs. The results suggested that the self-assembled FCNCs had preferred crystalline orientation. In combination with the microscopy observations, it was clear that the cellulose nano-flakes should have exposed (110) surfaces. On the other hand, the (110) diffraction peak exhibited obvious broadening, suggesting the length scale of the material along this direction was quite small, which also confirmed the two-dimensional characteristic of the material.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe FTIR spectra of MCC and nanocelluloses are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. Both MCC and nanocelluloses exhibited C-H stretching vibrations peaks at 2900 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The absorption peak of the O-H stretching vibration of microcrystalline cellulose was at 3346 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. In contrast, the FTIR spectra of CNCs and FCNCs showed an absorption peak of the O-H stretching vibration between 3425\u0026ndash;3444 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, indicating the hydrogen bonding stretching of type II cellulose (Zhang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). The shift reflected the weaker inter- and intrachain hydrogen bonds of the nanocelluloses. Furthermore, for microcrystalline cellulose, the 1430 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e band was relatively strong, whereas it weakened and shifted to 1416 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for nanocelluloses. This suggested that the conformation of the primary alcohol hydroxyl CH\u003csub\u003e2\u003c/sub\u003eOH at the C6 position in cellulose changes from trans-gauche (tg) to gauche-trans (gt), indicating the transition from cellulose type I to type II. The above characteristics in FTIR spectra all confirmed the crystalline structures of MCC, CNCs and FCNCs determined by XRD analysis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e, XPS was used to further investigate chemical compositions of the surfaces of CNCs, FCNCs, and SCNCs. All samples were primarily composed of carbon and oxygen atoms. The XPS C 1s spectrums of the three nanocelluloses all exhibited two distinct peaks with binding energies of 286.6, and 287.9-288.3 eV, corresponding to cellulose C-O, and O-C-O, respectively. Besides cellulose, C 1s also showed a peak with binding energies of 284.8 eV, corresponding to aliphatic carbons C-C/C-H(Yan et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). However, the O/C ratios varied from sample to sample. Compared with CNCs and SCNCs, the O/C ratio of FCNCs was significantly reduced. This observation might indicate a less presence of adsorbed water on the surface of FCNCs (Koljonen et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2003\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003eThermal properties of CNCs and FCNCs\u003c/h2\u003e \u003cp\u003eThe thermos gravimetric and derivative thermos gravimetric curves of microcrystalline cellulose and nanocelluloses are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. These cellulose nano-materials exhibited significantly different thermal characteristics relative to the MCC. Decomposition of the MCC initiated at the temperature of 257 ℃. The maximum weight loss appeared at 327 ℃. The onset decomposition temperatures and maximum weight loss temperatures of CNCs and FCNCs were lower than those of MCC. Specifically, CNCs had an onset decomposition temperature of 124\u0026deg;C and a maximum weight loss temperature of 180\u0026deg;C. The two characteristic temperatures for FCNCs were 167\u0026deg;C and 298\u0026deg;C, respectively. On the other hand, the nanocelluloses showed more gradual thermal transition. MCC lost nearly 82% of its mass between 300\u0026ndash;400\u0026deg;C, leaving only 7.4% ash at 600\u0026deg;C. In contrast, FCNCs lost 53% of their mass in the range of 167\u0026ndash;300\u0026deg;C, followed by approximately 24% of their mass between 300\u0026ndash;600\u0026deg;C, leaving 15% of their mass behind. CNCs lost 36% of their mass in the initial decomposition temperature range up to 300\u0026deg;C, and 30% of their mass between 300\u0026ndash;600\u0026deg;C. Meanwhile, CNCs retained more residue, close to about 30%. These major differences in thermal behaviors between the CNCs and the FCNCs might be attributed to variations in surface area, morphology, and particle size. The high surface area of nanocelluloses is a significant factor in reducing their thermal stability, as a consequence of the increased surface area exposed to heat (Lu and Hsieh \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). Furthermore, it was reported that the thermal degradation of one nanofiber could lead to degradation in neighboring nanofibers (Qui\u0026eacute;vy et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). It could be observed from SEM and TEM that, CNCs were smaller than FCNCs in size and had more contact with each other, which resulted in enhanced thermal conductivity. Moreover, due to the large-diameter flaky structure of FCNCs, fewer readily decomposable free end chains were formed on the surface of FCNCs relative to that of CNCs (Zhao et al. \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Consequently, FCNCs began to decompose at relatively high temperatures. Compared to CNCs, FCNCs were more thermally stable but had a lower carbon residual rate. The results suggested that FCNCs possess relatively better thermal stability. Additionally, both CNCs and FCNCs exhibited lower weight loss, which could potentially enhance the amorphous carbon yield.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003eSurface property of FCNCs\u003c/h2\u003e \u003cp\u003eThe above profile and structural features of nanocelluloses revealed that FCNCs had (110) exposed surfaces. The formation mechanism is analyzed as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. Cellulose is composed of alternating crystalline and amorphous regions. During hydrolysis, amorphous regions were preferentially hydrolyzed, whereas the crystalline domains were more predictable to be preserved to form CNCs (Habibi et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). Nevertheless, hydrolysis produced small-sized cellulose fragments that were dispersed in acid solutions due to the repulsive force of their surface negative charges. During dialysis, as the acidity of the solution diminishing, the H-bonding and van der Waals forces between the cellulose molecules gradually overcame the repulsive forces of the negative charges on their surfaces, resulting in aggregation and stacking (Lu and Hsieh \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). It has been demonstrated that cellulose type II structure is the most thermodynamic stability of molecular chains stacking. The H-bonding between the molecular chains precisely aligned the cellulose molecular chains along their crystallographic [1\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\stackrel{-}{1}\\)\u003c/span\u003e\u003c/span\u003e0] directions, resulting in a two-dimensional structure with (110) surface exposed. Then, the molecules between the (110) surfaces were stacked by van der Waals forces to form two-dimensional cellulose nanocrystals with a certain thickness (3\u0026thinsp;~\u0026thinsp;3.5 nm in the present case).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAccording to the atomic projection in the middle part in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e, each dehydrated glucose unit of the cellulose adopts a \u003csup\u003e1\u003c/sup\u003eC\u003csub\u003e4\u003c/sub\u003e chair conformation, with the all alcohol substituents in the ring plane, while the hydrogen atom in the vertical position. Therefore, in a manner analogous to the (200) surface of cellulose type I\u003csub\u003eβ\u003c/sub\u003e structure (Mazeau and Rivet \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), the (110) surface of cellulose type II structure exhibited a relatively hydrophobic characteristic, with the hydrophobic C-H moieties exposed to the surrounding medium. To confirm this deduction, contanct angle tests were used to evaluated the hydrophobicity of the FCNCs (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e). It was observed that the water contact angle on FCNC film was considerably larger than that on CNCs. The contact angle value for CNCs was found to be 43.5\u0026deg;, while that for FCNCs reached 72.0\u0026deg;. This finding indicated that FCNCs possess apparently hydrophobic surface. The results of the contact angle experiments reversely verified that the (110) surface was actually the main exposed surface of FCNCs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eThe flaky nanocelluloses were isolated using the waste liquor of CNCs prepared by acid hydrolysis. The FCNCs exhibit Cellulose type II crystalline structure with exposed (110) surface. The average diameters of FCNCs were 712 nm, with height between 3\u0026thinsp;~\u0026thinsp;3.5 nm. FCNCs were formed through self-assembly of low molecular weight cellulose chains via hydrogen-bonding between the molecular chains. Exposed (110) surfaces endow the new type of nanocellulose with hydrophobic property which was confirmed by contact angle tests. The water contact angle value was measured to be as high as 72.0\u0026deg;. Successful extraction of flaky nanocelluloses from the cellulose hydrolysis waste liquor not only reduces waste in production processes of cellulose nanocrystals, but also provide more possibilities for cellulose application owing to the unique structure and surface property.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements \u0026nbsp;\u003c/strong\u003eThis work is financially supported by the research foundation of SYNL (L2019F15). W.Z. and J.W. acknowledge the support by Liaoning Provincial Science and Technology Plan Project (No.2023-MS-067).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions \u0026nbsp;\u003c/strong\u003eAll authors contributed to the study conception and design. J.L., X.J., and G.G. conducted the experiments and wrote the main manuscript text. W.Z. and J.W. analyzed the data and modified the grammar. Y.Z. and D.L. instructed the experiments and revised the manuscript.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding \u0026nbsp;\u003c/strong\u003eThis work is supported by the research foundation of SYNL (L2019F15) and Liaoning Provincial Science and Technology Plan Project (No.2023-MS-067).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability \u0026nbsp;\u003c/strong\u003eThe data and materials of the manuscript can be obtained from the authors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval and consent to participate \u0026nbsp;\u003c/strong\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for publication \u0026nbsp;\u003c/strong\u003eAll authors\u0026nbsp;approve\u0026nbsp;to publish the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u0026nbsp;\u003c/strong\u003eThe authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eBeck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. 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Cellulose 26:8625\u0026ndash;8643. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10570-019-02683-8\u003c/span\u003e\u003cspan address=\"10.1007/s10570-019-02683-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Cellulose nanocrystals, Acid hydrolysis, Flaky morphology, Waste liquor recycling","lastPublishedDoi":"10.21203/rs.3.rs-4649995/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4649995/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIt is of great value to reuse of the dissolved carbohydrates from the spent liquor produced in the acid hydrolysis process of cellulose nanocrystals (CNCs). In the present study, a special flake-like nanocellulose crystals (FCNCs) were self-assembled from the dissolved cellulose chains with low molecular weight via a \"bottom-up\" approach. The average diameters of FCNCs were 712 nm, with thickness in the range of 3\u0026thinsp;~\u0026thinsp;3.5 nm. They exhibited superior thermal stability relative to CNCs. XRD characterization revealed that the FCNCs with the cellulose type II structure possessed the hydrophobic (110) plane as the exposed surface which endowed the material with relatively hydrophobic property. Confirmed by the contact angle tests, the water contact angle value of FCNCs film was as high as 72.0\u0026deg;, almost twofold of that of CNCs film.\u003c/p\u003e","manuscriptTitle":"Preparing flake nanocelluloses with hydrophobic surface from the spent liquor of cellulose nanocrystals","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-29 17:42:26","doi":"10.21203/rs.3.rs-4649995/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-07-04T15:13:14+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-07-04T13:42:53+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-07-04T13:42:15+00:00","index":"","fulltext":""},{"type":"submitted","content":"Cellulose","date":"2024-06-27T07:13:07+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"61cfb418-edce-402f-a826-dc00b04fde6c","owner":[],"postedDate":"July 29th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-02-10T16:04:14+00:00","versionOfRecord":{"articleIdentity":"rs-4649995","link":"https://doi.org/10.1007/s10570-025-06388-z","journal":{"identity":"cellulose","isVorOnly":false,"title":"Cellulose"},"publishedOn":"2025-02-03 15:58:00","publishedOnDateReadable":"February 3rd, 2025"},"versionCreatedAt":"2024-07-29 17:42:26","video":"","vorDoi":"10.1007/s10570-025-06388-z","vorDoiUrl":"https://doi.org/10.1007/s10570-025-06388-z","workflowStages":[]},"version":"v1","identity":"rs-4649995","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4649995","identity":"rs-4649995","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}