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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

Fluorescent Eu-MOF@nanocellulose-based nanopaper for rapid and sensitive detection of uranium (Ⅵ)

Yuqing Deng,Shan Jiang,Zifei Yan,Youlu Chu,Weibing Wu,Huining Xiao

Radioactive uranium leaks into natural water bodies mainly in the form of uranyl ions (UO 2 2+ ), posing ecological and human health risks. Fluorescent europium-based metal-organic frameworks (Eu-MOFs) have been demonstrated to be effective fluorescent sensors for UO 2 2+ , but the large size, powder state and poor dispersity limit their further application. In this work, fluorescent Eu-MOFs were in-situ grown on TEMPO-oxidized cellulose nanofibers (TOCNFs), which is the first time that spherical Eu-MOF crystals with sizes below 10 nm were prepared. Fluorescence spectral analysis revealed a nine-fold increase in the fluorescence intensity of TOCNF@Eu-MOF compared to Eu-MOF. The nanocomposites achieved rapid and sensitive fluorescence quenching to UO 2 2+ through the “antenna effect” and unsaturated Lewis basic sites on the ligands binding with UO 2 2+ . Moreover, TOCNF@Eu-MOF demonstrated excellent selectivity and anti-interference for UO 2 2+ detection. For the nanopaper-based sensor made from TOCNF@Eu-MOF, the Stern-Volmer quenching constant ( K SV ) was calculated as 8.21 × 10 4  M −1 , and the lowest limit of detection (LOD) was 6.6 × 10 −7  M, significantly lower than the 1.32 × 10 −6  M of Eu-MOFs. In addition, the nanopaper exhibited good fluorescence stability and cyclic detection performance, enabling the rapid and convenient detection of UO 2 2+ in the aqueous phase within 30 s by simple dipping.

CAS / MDL: 63557-10-8
研究领域: 材料科学 · 环境科学
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CARBOHYDRATE POLYMERS · 2019 · IF 6.044

Facile and quick formation of cellulose nanopaper with nanoparticles and its characterization

Limei Ma,Zijian Xu,Xiangzhi Zhang,Jinyou Lin,Renzhong Tai

Cellulose nanofibrils (CNF) is a suitable functional material as its lightweight, huge availability and biodegradable advantages. A direct-evaporation method was employed to prepare the CNF nanopapers with or without Fe 3 O 4 and TiO 2 nanoparticles (NPs) in the form of films, which is more facile and efficient in comparison with the methods of vacuum-filtration and cast drying. A combination of three-dimensional (3D) focal stacks and dual-energy imaging method was firstly used to characterize the CNF nanopapers embedded with Fe 3 O 4 and TiO 2 NPs, where the locations of the NPs can be clearly and exactly distinguished. Furthermore, the thickness, transparency, magnetism and tensile properties of the CNF nanopapers were characterized. This work shows a facile method for the preparation of CNF nanopapers with or without addition. More importantly, the combination of focal stacks and dual-energy imaging method offers a superior means of characterizing the spatial structures and 3D elemental visualization.

CAS / MDL: 13463-67-7
研究领域: 材料科学 · 生物医学工程
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

In Situ Lignin Modification Enabling Enhanced Interfibrillar Interactions in Lignocellulosic Nanomaterials toward Structural Applications

Shan Jiang,Xiuyu Liu,Zehai Wang,Lin Zhou,Zhiqian Meng,Xinyi Wang,Guoning Chen,Shuangfei Wang,Yan Jiang

Lignocellulose nanopaper (LNP) assembled from lignocellulose nanofibrils (LCNFs) is an emerging eco-friendly structural material applicable to a variety of fields. Lignin serves as a crucial functional component in the LNP matrix; however, it negatively affects the interfacial hydrogen-bonding behaviors among LCNFs and consequently the inferior mechanical performance of LNP. In this study, a mild ozone-oxidation strategy was used to modify lignin macromolecules in situ without significant degradation of carbohydrate polymers (i.e., cellulose and hemicellulose) in LCNFs whereupon the interfacial hydrogen-bond energy was dramatically improved in the assembly and deformation process of LNP as validated by molecular dynamics simulation. Consequently, the lignin-modified LNP exhibited significantly enhanced tensile strength (from 83 to 140 MPa) and toughness (from 1.9 to 7.1 J/m3), which even surpassed those of conventional cellulose nanopaper. Benefiting from the well-preserved lignocellulosic structure, lignin-modified LNP maintained its inherent favorable water and thermal stability and intriguing optical performance, which supported our developed LNP to be a multifunctional structural material for diversified fields, for example, flexible electronic applications. Additionally, the estimated production cost for our developed LNP was approximately half of that for conventional cellulose nanopaper due to its significantly lower resource inputs such as the material, water, and energy. Overall, our study provides a site-specific macromolecular modulation strategy for the economically and environmentally feasible fabrication of high-performance lignocellulosic nanomaterials toward advanced structural applications.

研究领域: 材料科学 · 林业工程 · 环境科学
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CARBOHYDRATE POLYMERS · 2023 · IF 11.2

Mechanically strong nanopapers based on lignin containing cellulose micro- and nano-hybrid fibrils: Lignin content-fibrils morphology-strengthening mechanism

Jiran Dong,Jinsong Zeng,Pengfei Li,Jinpeng Li,Bin Wang,Jun Xu,Wenhua Gao,Kefu Chen

Lignin-containing cellulose nanopapers are emerging multifunctional materials in the fields of coatings, films, and packaging. However, the forming mechanism and properties of nanopapers with various lignin content have not been thoroughly studied. In this work, a mechanically strong nanopaper was fabricated based on lignin-containing cellulose micro- and nano-hybrid fibrils (LCNFs). The influence of lignin content and fibrils morphology on the formation process of nanopapers was investigated to understand the strengthening mechanism of nanopapers. LCNFs with high lignin content provided nanopapers with intertwined micro- and nano-hybrid fibrils layers with small layer spacing, while LCNFs with low lignin content offered nanopapers interlaced nanofibrils layers with large layer spacing. Although lignin was expected to interfere with hydrogen bonds between fibrils, the uniformly distributed lignin contributed to the stress transfer between fibrils. Due to the good coordination between microfibrils, nanofibrils and lignin (as network skeleton, filler and natural binder, respectively), the well-designed LCNFs nanopapers with lignin content of 14.5 % showed excellent mechanical properties, including tensile strength (183.8 MPa), Young's modulus (5.6 GPa) and elongation (9.2 %). This work deeply reveals the relationship between lignin content, morphology and strengthening mechanism of nanopapers, and providing theoretical guidance for employing LCNFs as structural and reinforcing materials to design robust composites.

研究领域: 材料科学 · 林业工程 · 生物质材料
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RSC Advances · 2016 ·Vol. 6 ·期 68 ·63171-63177 · IF 3.289

Hierarchical alginate biopolymer papers produced via lanthanide ion coordination

Shunli Liu,Jun Ling,Kewen Li,Fang Yao,Olayinka Oderinde,Zhihong Zhang,Guodong Fu

Inspired by the heterogeneous architectures of biological composites, mimicking the hierarchical structure of nacre is a powerful strategy to construct high-performance materials. This paper presents a lightweight and nacre-like hierarchical paper which was fabricated via lanthanide ion coordination. Sodium alginate (SA) biopolymers and lanthanide ions (Nd3+, Gd3+, Ce3+ and Yb3+) were used as ideal building blocks and connection points, respectively. SA biopolymers and lanthanide ions rapidly self-assembled into an aligned hydrogel. The synthesized hydrogel was subsequently dried to form layered alginate-based papers. The formation mechanism of the layered paper was investigated and demonstrated that lanthanide ion coordination can produce the hierarchical structure. The as-prepared layered SA–Nd(III) nanopaper exhibited a high strength of 124.2 ± 5.2 MPa, toughness of 8.2 ± 0.4 MJ m−3, and Young's modulus of 5.2 ± 0.2 GPa, as well as excellent resistance to solvents. Owing to their outstanding mechanical properties and easy and fast fabrication, the layered SA–Nd(III) papers demonstrated a potential application in the fields of biomaterials. This new strategy based on lanthanide ion coordination, can also be used to construct integrated, high-performance, and biopolymer materials.

研究领域: 材料科学 · 生物材料
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Heat-triggered shape recovery, EMI shielding and flame retardant: A novel cellulose/M(OH)(OCH3)@dopamine@Ag (M=Co, Ni) nanopaper for early fire alarm

Xiang Dong,Guo-wei Dai,Le Xie,De-long Li,Zhiyu Sun,Song Liu

Fire alarm systems are essential for protecting lives and properties from fire hazards. However, most of the existing fire alarm nanopapers rely on the resistance reduction after heating, which requires direct contact with the flame. In this study, we present a novel fire alarm nanopaper (CMPA) based on heat-triggered shape recovery. The CMPA is composed of hydroxypropyl methyl cellulose (HPMC) as the matrix and 2D nanomaterials M(OH)(OCH 3 ) as fillers. When the temperature of CMPA exceeded the glass transition, the thrice-folded CMPA-1.0 flattened in 30s and connected to the alarm circuit based on its conductive surface. According to the results, the CMPA-1.0 with a thickness of about 0.2 mm had an efficient electromagnetic shielding of 42.1 dB. Moreover, the CMPA-1.0 self-extinguished rapidly after being ignited with its original shape preserved. The peak heat release rate of CMPA-1.0 was 108.9 W/g, which was 61.9 % lower than that of HPMC. Furthermore, the thermal conductivity of CMPA-1.0 reached to 0.317 W m −1  K −1 , which was 40.8 % higher than that of HPMC, reducing the heat accumulation effectively. This work shows that CMPA is an ideal material for sensitive and safe early fire alarm, and the strategy based on heat-triggered shape recovery is promising in fire alarm application.

研究领域: 材料科学 · 消防安全
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Hemicellulose phase synergistically boosting the tribopositivity of cellulose nanopaper: Effectiveness and mechanism

Yan Jiang,Mengmeng Yang,Liyun Cheng,Lu Xiao,Xinyi Wang,Ruixuan Liu,Yiyan Wu,Shuangfei Wang,Xiuyu Liu

The integration of lignocellulosic nanomaterials into energy management applications possesses enormous technical appeals catering to high-tech and low-carbon era. Nature has designed hierarchical and heterogeneous lignocellulose microstructure, which can be harnessed for desirable dielectric behaviors towards specific applications. Here, we make the first attempt to boost the tribopositivity of 2D self-assembly (i.e., nanopaper) of cellulose nanofibrils by leveraging the inherent functionality of their hemicellulose phase. In comparison to conventional nanopapers assembled from TEMPO-oxidized/enzymatic cellulose nanofibrils with significantly lower hemicellulose content (4.6/12.2 vs. 20.3 wt%), the as-prepared hemicellulose-rich nanopaper exhibits ~2-fold higher electron-donating capability, which in turn generates ~1.5-fold higher triboelectric nanogenerator (TENG) output when paired with given tribonegative materials. We provide multiscale insights into the boosted tribopositivity of nanopaper by hemicellulose phase arising from its unique molecular structure and micro-distribution pattern. Furthermore, amorphous hemicellulose phase can be readily molecularly designed, e.g., aminosilanization, which further enhances the tribopositivity of nanopaper towards self-powered applications requiring high energy density. Besides, the hemicellulose-rich nanopaper is highly writable, mechanically strong, and optically transparent, serving as a desired structural material with favorable programmability for various TENG-based sensing, encryption and wearable devices.

研究领域: 材料科学 · 生物基材料 · 能源技术
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Mechanically Strong Electrically Insulated Nanopapers with High UV Resistance Derived from Aramid Nanofibers and Cellulose Nanofibrils

Fugang Hu,Jinsong Zeng,Jinpeng Li,Bin Wang,Zheng Cheng,Tianguang Wang,Kefu Chen

Aramid nanofibers (ANFs) have great potential for civil and military applications due to their remarkable mechanical modulus, excellent chemical reliability, and superior thermostability. Unfortunately, the weak combination of neighboring ANFs limits the mechanical properties of ANF-based materials owing to their inherent rigidity and chemical inertness. Herein, high-performance nanopapers are fabricated by introducing a tiny amount of cellulose nanofibrils (CNFs) to serve as reinforcing blocks via vacuum filtration. As a result of the formation of nanosized building blocks and hydrogen-bonding interaction of CNFs, the resultant ANF/CNF nanopaper yields a record-high tensile strength (406.43 ± 16.93 MPa) and toughness (86.13 ± 5.22 MJ m–3), which are 1.8 and 4.3 times higher than those of the pure ANF nanopaper, respectively. When normalized by weight, the specific tensile strength of the nanopaper is as high as 307.90 MPa·g–1·cm3, which is even significantly superior to that of titanium alloys (257 MPa·g–1·cm3). The ANF/CNF nanopaper also possesses excellent dielectric strength (53.42 kV mm–1), superior UV-shielding performance (≥99.999% absorption for ultraviolet radiation), and a favorable thermostability (Tonset = 530 °C). This study proposes a new design strategy for developing ultrathin ANF-based nanopapers combined with high reliability and thermostability for application in high-end electrical insulation fields, such as 5G communication, wearable electronics, and artificial intelligence.

研究领域: 材料科学 · 纳米技术 · 电气工程
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IONICS · 2018 ·Vol. 25 ·期 2 ·573-581 · IF 2.347

Facile fabrication of holey graphene oxide paper bonded with sulfonic acid for highly efficient proton conduction

Zhang Chengyi,Zhang Wen,Mu Yingxin,Fang Feifei,Huang Chengde,Wang Yuxin

In this work, a novel holey graphene oxide bonded with sulfonic acid groups (S-HGO) was developed using a facile and eco-friendly strategy: erosion and oxidation of graphene oxide (GO) by H 2 O 2 and sulfonation by 4-benzenediazoniumsulfonate. The freestanding paper fabricated by S-HGO shows a high proton conductivity of 4.97 × 10 −2  S cm −1 at 60 °C and 100% relative humidity (RH), which is comparable to Nafion 115 (7.67 × 10 −2  S cm −1 ) at the same condition. The holes on S-HGO provide shortcut channels for proton transfer across the GO nanosheet. The chemical-linked sulfonic acid groups afford additional hop sites for proton conduction and endow itself an enhanced thermostability. Under 100% RH and ambient pressure, the freestanding S-HGO deliver a peak power density of 103 mW cm −2 at a load current density of 273 mA cm −2 , which is about three times more than that of GO at 35 °C. The results demonstrate that this S-HGO paper is a promising nanoscale inorganic material for proton exchange membranes.

研究领域: 材料科学 · 能源科学
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GREEN CHEMISTRY · 2020 ·Vol. 22 ·期 10 ·3208-3215 · IF 9.48

Transparent, flexible and recyclable nanopaper-based touch sensors fabricated via inkjet-printing

Hao Ling,Ruwei Chen,Quanbo Huang,Feng Shen,Yuyuan Wang,Xiaohui Wang

Transparent, flexible, and eco-friendly touch sensors are important components for next-generation green electronics such as wearable sensors and e-skins. However, most current touch sensors, which are based on plastics or glass substrates and indium tin oxide or metal microelectrodes, are not environmentally friendly, as well as being difficult to recycle and expensive. Here, we demonstrate that a green, transparent, flexible, and recyclable nanopaper-based touch sensor (NPTS) can be fabricated via inkjet printing a conductive polymer, poly(3,4-ethylene dioxythiophene)-doped polystyrene sulfonate (PEDOT:PSS), on cellulose nanofibril paper. The materials cost of a single-keypad NPTS with a size of 3.5 cm × 2.5 cm × 0.05 mm is only $0.060. Good printability, excellent transparency (80% at 400 nm), and high conductivity (1360 S cm−1) were achieved with the PEDOT:PSS microelectrodes when using a newly developed, eco-friendly water-based ink formulation. It takes only 3–4 weeks for the NPTS to degrade completely in natural soil. A four-keypad NPTS was demonstrated by interfacing with the Arduino UNO development board. Folding, bending, and multiple finger-touch trials caused only slight capacitive changes to the NPTS, with no loss of function. The facile fabrication of the NPTS will be invaluable for many practical applications where eco-friendly, transparent, flexible, durable, recyclable, and economical touch-control is required.

CAS / MDL: 2564-83-2
研究领域: 材料科学 · 电子工程 · 环境科学
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Facile Microembossing Process for Microchannel Fabrication for Nanocellulose-Paper-Based Microfluidics

Wenwen Yuan,Hang Yuan,Keran Jiao,Jia Zhu,Eng Gee Lim,Ivona Mitrovic,Sixuan Duan,Yongjie Wang,Shan Cong,Chun Zhao,Jie Sun,Xinyu Liu,Pengfei Song

Nanofibrillated cellulose paper (nanopaper) has gained growing interest as one promising substrate material for paper-based microfluidics, thanks to its ultrasmooth surface, high optical transparency, uniform nanofiber matrix with nanoscale porosity, and tunable chemical properties. Recently, research on nanopaper-based microfluidics has quickly advanced; however, the current technique of patterning microchannels on nanopaper (i.e., 3D printing, spray coating, or manual cutting and sticking), that is fundamental for application development, still has some limitations, such as ease-of-contamination, and more importantly, only enabling millimeter-scale channels. This paper reports a facile process that leverages the simple operations of microembossing with the convenient plastic micro-molds, for the first time, patterning nanopaper microchannels downing to 200 μm, which is 4 times better than the existing methods and is time-saving (<45 mins). We also optimized the patterning parameters and provided one quick look-up table as the guideline for application developments. As proof-of-concept, we first demonstrated two fundamental microfluidic devices on nanopaper, the laminar-mixer and droplet generator, and two functional nanopaper-based analytical devices (NanoPADs) for glucose and Rhodamine B (RhB) sensing based on optical colorimetry and surface-enhanced Raman spectroscopy, respectively. The two NanoPADs showed outstanding performance with low limits of detection (2 mM for glucose and 19fM for RhB), which are 1.25× and 500× fold improvement compared to the previously reported values. This can be attributed to our newly developed highly accurate microchannel patterning process that enables high integration and fine-tunability of the NanoPADs along with the superior optical properties of nanopaper.

CAS / MDL: 16940-66-2
研究领域: 材料科学 · 分析化学 · 生物医学工程
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CELLULOSE · 2016 ·Vol. 23 ·期 2 ·1375-1382 · IF 3.195

Comparative study of the structure, mechanical and thermomechanical properties of cellulose nanopapers with different thickness

Li Qing,Chen Wenshuai,Li Yanna,Guo Xiaoyu,Song Shan,Wang Qingwen,Liu Yixing,Li Jian,Yu Haipeng,Zeng Jie

This article describes the comparative study of the structure, mechanical and thermomechanical properties of cellulose nanopapers with different thicknesses. Cellulose nanopapers were fabricated by vacuum-filtering cellulose nanofiber (CNF) suspensions. The surfaces of the nanopapers consisted of long and entangled CNFs (10–30 nm in width) and their aggregates, while cross-sections exhibited parallel aligned lamellar structures. The nanopaper thickness can be tailored by controlling the amounts of CNF suspensions used for filtration. Owing to the packing density of CNFs, nanopapers with different thicknesses had similar densities of ~1.50 g cm −3 . The thin nanopapers were transparent and flexible. With increasing thickness, the Young’s modulus of the nanopapers slightly decreased, while the ultimate strain and work of fracture increased. The thicker nanopapers displayed higher storage and loss modulus. The nanopapers still kept advantageous mechanical properties even at high temperatures around 260 °C because of the high thermal stability of CNFs and their strong entangled web-like structures.

研究领域: 材料科学 · 纳米技术
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