2020 - Zhang - Methods and Applications of Nanocellulose Loaded With Inorganic Nanomaterials - A Review

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Carbohydrate Polymers 229 (2020) 115454

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Methods and applications of nanocellulose loaded with inorganic T


nanomaterials: A review

Qing Zhanga, Lei Zhangc, Weibing Wua,b, , Huining Xiaod
a
Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab of Pulp & Paper Science & Technology, Nanjing
Forestry University, Nanjing 210037, China
b
State Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of Sciences, Jinan 250353, China
c
Key Laboratory for Organic Electronics and information, National Jiangsu Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts &
Telecommunications, Nanjing 210023, China
d
Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3, Canada

A R T I C LE I N FO A B S T R A C T

Keywords: Nanocellulose obtained from natural renewable resources has attracted enormous interests owing to its unique
Nanocellulose morphological characteristics, excellent mechanical strength, biocompatibility and biodegradability for a variety
Inorganic nanoparticle of applications in many fields. The template structure, high specific surface area, and active surface groups make
Nanocomposite it feasible to conduct surface modification and accommodate various nano-structured materials via physical or
Method
chemical deposition. The review presented herein focuses on the methodologies of loading different nano-
Application
structured materials on nanocellulose, including metals, nanocarbons, oxides, mineral salt, quantum dots and
nonmetallic elements; and further describes the applications of nanocellulose composites in the fields of cata-
lysis, optical electronic devices, biomedicine, sensors, composite reinforcement, photoswitching, flame re-
tardancy, and oil/water separation.

1. Introduction flexible, consisting of alternating crystalline and amorphous regions


(Saito, Kimura, Nishiyama, & Isogai, 2007). There are also many sy-
With the emergence of global resource shortages and environmental nonyms employed to define NFC in the literatures, such as micro-
problems, there is a growing demand for more environmentally friendly fibrillated cellulose (Lavoine, Desloges, Dufresne, & Bras, 2012), mi-
and renewable raw materials. Cellulose, as a sustainable and renewable crofibril aggregates, nanofibrillated cellulose (Li et al., 2014),
resource, has attracted much attention and stimulated researchers to nanofibre, nanofibril (Jung et al., 2015) and nanofibrillar cellulose
develop cellulose-based materials with novel functions. Cellulosic ma- (Hakkarainen et al., 2016). BNC, the nanofiber material with high-
terials with nanometer size at least in one dimension are referred to as crystallinity high-purity and the diameter in the range of 30–100 nm
nanocellulose. Nanocellulose mainly includes nanocrystalline cellulose and variable lengths, is obtained by the fermentation in the presence of
(NCC), nanofibrillar cellulose (NFC) and bacterial nanocellulose (BNC). microorganisms such as acetobacter xylinum (Czaja, Young, Kawecki, &
Among them, NCC consists of rod-like cellulose crystals with widths of Brown, 2007). From a resource point of view, nanocellulose is mainly
3–20 nm and lengths between 100 and 350 nm, respectively (Beck- derived from abundant plant fiber, which has the advantages of re-
Candanedo, Roman, & Gray, 2005; Klemm et al., 2011). It is also named newable, intrinsically biodegradable and biocompatible. In terms of
cellulose nanocrystal, cellulose whisker, nanowisker, nanowire and properties, nanocellulose also has the advantages of high aspect ratio,
nanorod due to the elongated and rod-like shape (Xue, Mou, & Xiao, large specific surface area, high hydrophilicity, high transparency, high
2017). Removing the amorphous regions in natural cellulose while re- strength, high Young's modulus, and low thermal expansion coefficient
taining the crystalline regions provides NCC in powder, liquid or gel (Kontturi et al., 2018; Moon, Martini, Nairn, Simonsen, & Youngblood,
state (Wu & Zhang, 2014). NFC is generally prepared by mechanical or 2011).
chem-mechanical methods and has a fibrillar shape with a diameter of Nanocellulose has aroused wide interests in the field of materials
5–60 nm and several microns in length (Ifuku & Yano, 2015). NFC is science, and can be used as an independent functional material,


Corresponding author at: Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab of Pulp & Paper
Science & Technology, Nanjing Forestry University, Nanjing 210037, China.
E-mail address: wbwu@njfu.edu.cn (W. Wu).

https://doi.org/10.1016/j.carbpol.2019.115454
Received 17 July 2019; Received in revised form 14 September 2019; Accepted 6 October 2019
Available online 13 October 2019
0144-8617/ © 2019 Elsevier Ltd. All rights reserved.
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

template support or reinforcement unit in composite materials. 2. Deposition of nanoparticles on nanocellulose


Moreover, nanocellulose retains the structure and properties of pri-
mordial cellulose, containing a large number of reactive groups on the 2.1. Metals
surface, which enables it to be modified by physical adsorption (Chi &
Catchmark, 2017; Guan et al., 2018; Salajkova, Berglund, & Zhou, In the past few decades, metal nanoparticles have attracted wide
2012), covalent bonding (Missoum, Belgacem, Barnes, Brochier-Salon, attention in many fields due to their unique optical, electrical proper-
& Bras, 2012; Montanari, Rountani, Heux, & Vignon, 2005; Wu, Song ties and good catalytic effects. Metal nanoparticles usually become
et al., 2018) and surface graft polymerization (Lonnberg, Fogelstrom, thermodynamically unstable and tend to aggregate because of their
Berglund, Malmstrom, & Hult, 2008; Wu et al., 2015) to further im- large specific surface area. Nanocellulose has been reported to possess
prove the performance. A number of reviews on the preparation good stabilizing effect for metal nanoparticles, which can promote the
(Klemm et al., 2011; Nechyporchuk, Belgacem, & Bras, 2016), mod- nucleation of nanoparticles as well as prevent their agglomeration
ification (Habibi, 2014; Khalil et al., 2014) and applications (Klemm (Huang, Gray, & Li, 2013; Kaushik, Basu et al., 2015). At present, the
et al., 2018; Thomas et al., 2018; Xue et al., 2017) of nanocellulose are deposition of metal nanoparticles on nanocellulose is mainly achieved
available for reference. The unique morphology and reactive groups by physical adsorption and chemical reduction synthesis. Various metal
make nanocellulose good biological template to carry out in situ nanoparticles including noble and non-noble, such as gold (Au) (Azetsu,
synthesis and physical deposition of nanoparticles. After the loading of Koga, Isogai, & Kitaoka, 2011; Fan, Liang, Zhang, & Xu, 2018; Jesus,
nano-structured materials on nanocellulose, the obtained nanocompo- Laura, Ruiz-Palomero, & Valcarcel, 2018; Lam, Hrapovic, Majid, Chong,
sites are rendered unique properties owing to synergistic effect, which & Luong, 2012; Wei & Vikesland, 2015; Wei, Rodriguez, Renneckar,
are unachievable by nano-structured materials alone. However, few Leng, & Vikesland, 2015; Wu et al., 2014), silver (Ag) (Barud et al.,
reviews have paid close attention to this aspect over the past years. 2011; Diez et al., 2011; Dong, Snyder, Tran, & Leadore, 2013; Fortunati,
Therefore, the main focuses of the current review are the methods of Mattioli, Armentano, & Kenny, 2014; Hoeng, Denneulin, Neuman, &
loading inorganic nanoparticles on nanocellulose, including metals, Bras, 2015; Hoeng, Bras, Gicquel, Krosnicki, & Denneulin, 2017; Liu,
non-metals, oxides, mineral salt, quantum dots and nonmetallic sub- Wang, Song, & Shang, 2011; Lokanathan, Uddin, Rojas, & Laine, 2014;
stance to create innovative and green-based nanocomposites. The ap- Ramaraju, Imae, & Destaye, 2015; Son, Youk, & Park, 2006), nickel (Ni)
plications of such nanocomposites in the fields of catalysis, optical (Shin, Bae, Arey, & Exarhos, 2007), ruthenium (Ru) (Gopiraman et al.,
electronic devices, biomedicine, sensors, composite reinforcement, 2015; Kaushik, Friedman et al., 2015; Yamaguchi & Mizuno, 2002),
photoswitching, flame retardancy, and oil/water separation are also palladium (Pd) (Cirtiu, Dunlop-Briere, & Moores, 2011), platinum (Pt)
extensively reviewed (see Fig. 1). (Benaissi, Johnson, Walsh, & Thielemans, 2010; Johnson, Thielemans,
& Walsh, 2011; Lin et al., 2011), copper (Cu) (Bendi & Imae, 2013;
Eivazihollagh et al., 2017), iron (Fe) (Nadagouda & Varma, 2007) and
etc., have been loaded or assembled on nanocellulose. Tables 1–4
summarize the methods of loading various inorganic nanoparticles on
nanocellulose.

Fig. 1. Applications of nanocelluloe loaded with inorganic nanoparticles.

2
Table 1
The synthesis methods and applications of metal nanoparticles/nanocellulose composites.
Inorganic nanoparticles (size in nm) Precursor and synthesis method Substrate Application Ref.
Q. Zhang, et al.

Noble metal
AuNPs (10–30 nm) HAuCl4/ in situ reduction by NCC NCC Catalytic reduction of 4-nitrophenol to 4-aminophenol Wu et al., 2014
AuNPs (35 nm) HAuCl4/ in situ reduction by Na3Cit sulfonated NCC Detection of AuNPs Jesus et al., 2018
AuNPs (63 ± 17 nm) HAuCl4/ in situ reduction by sodium citrate tribasic BNC SERS detection of carbamazepine and atrazine Wei & Vikesland, 2015
dihydrat
AuNPs (20.5 ± 2.2 nm) HAuCl4/ in situ reduction by sodium citrate tribasic BNC SERS detection of MGITC,R6G and the environmental contaminant Wei et al., 2015
dihydrat atrazine
AuNPs (3 nm) HAuCl4/ electrostatic adsorption NCC Catalytic reduction of 4-nitrophenol to 4-aminophenol Lam et al., 2012
Au/Pd NPs (4-7 nm) HAuCl4/ in situ reduction by NaBH4 TEMPO-oxidized NCC Catalytic reduction of 4-nitrophenol to 4-aminophenol Azetsu et al., 2011
AuNP (41 nm/24 nm) HAuCl4/ filtration NFC SERS detection of hazardous chemical detection Kim et al., 2018
AuNP (40 nm) HAuCl4/ deposition and drying NFC SERS detection of 4-aminothiophenol Zhang et al., 2015
AuNP (18-25 nm), AgNPs(6-35 nm) HAuCl4, AgNO3/ in situ reduction by ascorbic acid NCC Catalytic reduction of 4-nitrophenol to 4-aminophenol Eisa et al., 2018
AuNP (2-4 nm) HAuCl4/ in situ reduction by NaBH4 or PDA NCC Catalytic reduction of 4-nitrophenol to 4-aminophenol Chen et al., 2015
AuNP (2-7 nm) HAuCl4 / in situ reduction by NaBH4 NCC Enzyme Immobilization Mahmoud et al., 2009
AuNP (2 nm) Electrostatic stabilization NCC Enzyme Immobilization Incani et al., 2013
AuNP (∼30 nm) HAuCl4/ in situ reduction by Na3Cit NCC Bifunctional nanofillers of mechanical and photothermal Hu et al., 2017
properties
AuNP (4.5 and 7.1 nm) HAuCl4/ in situ reduction by NaBH4 NCC Plasmonic sensor Schlesinger et al., 2015
AuNP (9 nm) HAuCl4/ in situ reduction by PEI BNC H2O2 biosensor Zhang et al., 2010
AuNPs(∼20 nm) HAuCl4/ in situ reduction by BNC BNC SERS detection of 4-fluorobenzenethiol and phenylacetic acid Wu et al., 2012
AuNPs(15-30 nm), Pd NPs(∼20 nm) HAuCl4, PdCl2/ in situ reduction by dialdehyde NFC NFC Catalysts for suzuki coupling reaction Zhang et al., 2018
AgNPs(20-80 nm) Ag powder/ electrostatic adsorption NCC – Fortunati et al., 2014
AgNPs(2 nm) AgNO3/ in situ reduction by NFC TEMPO-oxidized NFC – Dong et al., 2013
AgNPs (1-5 nm,) AgNO3/ in situ reduction by NaBH4 sulfonated NCC – Lokanathan et al., 2014
AgNPs (10-80 nm) AgNO3/ in situ reduction by NaBH4 TEMPO-oxidized NCC – Hoeng et al., 2015

3
AgNPs (64 ± 16 nm) AgNO3/ in situ reduction by NaBH4 TEMPO-oxidized NCC Conductive ink Hoeng et al., 2017
AgNP (11-12 nm) AgNO3/ stabilization by gold-thiol interaction NCC IR-actuated shape-memory Toncheva et al., 2018
AgNPs (<30 nm) AgNO3/ in situ reduction by triethanolamine BNC Antibacterial materials Barud et al., 2011
AgNPs (∼6.2 nm) AgNO3/reduction by triethanolamine and stabilization by TEMPO-oxidized NFC Environmental conservation (redox reduction degradation of Ramaraju et al., 2015
covalent bond Rhodamine B)
AgNPs AgNO3/ electrostatic adsorption NFC Fluorescence and antibacterial activity Diez et al., 2011
AgNPs (<10 nm) AgNO3/ in situ reduction by NaBH4 TEMPO-oxidized NCC Electrochemical detection of DNA hybridization Liu et al., 2011
AgNPs (300−600 nm) AgNO3/ in situ reduction by Na3Cit TEMPO-oxidized NFC SERS detection of p-aminothiophenol Nabeela et al., 2016
AgNPs (∼10 nm) AgNO3/ in situ reduction by PDA NCCs Catalytic reduction of 4-nitrophenol to 4-aminophenol Tang et al., 2015
AgNPs (5-25 nm) Tollen’s reagent / in situ reduction by glucose NCC Detection of Nonenzymatic Glucose and antibacterial activity Wang et al., 2016
AgNPs (4-5 nm) AgNO3/ in situ reduction by NCC NCC Antibacterial activity Xiong et al., 2013
AgNPs (<10 nm) AgNO3/ in situ reduction by NaBH4 TEMPO-oxidized NCC Bifunctional nanofillers of mechanical and antibacterial properties Liu, Song et al., 2012
AgNPs (20–45 nm) AgNO3/ in situ reduction by NCC NCC Antibacterial activity Drogat et al., 2011
AgNPs (1–20 nm) AgNO3/ in situ reduction by NCC NCC – Padalkar et al., 2010
AgNPs (16 ± 3 and 22 ± 7 nm) AgNO3/ in situ reduction by leaf extract of Syzygium NCC Wound dressings Singla et al., 2017
cumini
AgNPs (> 15 nm) AgNO3/ in situ reduction by NaBH4 NCC Catalytic reduction of 4-nitrophenol to 4-aminophenol An et al., 2017
AgNPs (20–80 nm) Ag nanopowder/ electrostatic adsorption NCC – Fortunati, Armentano, Zhou, Puglia et al.,
2012
AgNPs (20–80 nm) Ag nanopowder/ electrostatic adsorption NCC Morphological, mechanical, thermal and antibacterial response Fortunati, Armentano, Zhou, Iannoni et al.,
2012
+
AgNPs (40 ± 12.4 nm) Ag / in situ reduction by glucose NFC Antibacterial materials Martins et al., 2012
AgNPs (4–20 nm) AgNO3/ in situ reduction by UV irradiation NFC Antibacterial materials Xiao et al., 2013
AgNPs (∼16.5 nm) AgNO3/ in situ thermal reduction TEMPO-oxidized BNC Wound dressing Wu, Fuh et al., 2018
AgNPs AgNO3/ stabilization by gold-thiol interaction NCC-SH – Lokanathan et al., 2013
AgNPs (10–50 nm) AgNO3/ in situ reduction by BNC BNC Optical sensing of cyanide ion and 2-mercaptobenzothiazole Golmohammadi et al., 2017
AgNPs (10 ± 7 nm) AgNO3/ in situ reduction by BNC BNC Visual detection of volatile compounds Heli et al., 2016
AgNPs (10 ± 7 nm) AgNO3/ in situ reduction by Na3Cit BNC SERS detection of thiosalicylic acid and 2,2’-dithiodipyridine Marques et al., 2008
AgNPs AgNO3/ in situ reduction by NFC and Na3Cit NCF SERS detection of carbendazim Huang et al., 2019
(continued on next page)
Carbohydrate Polymers 229 (2020) 115454
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

2.1.1. Noble metal nanoparticles


There have been numerous reports on the use of nanocellulose to
load noble metal nanoparticles of Au (Azetsu et al., 2011; Eisa,
Abdelgawad, & Rojas, 2018; Jesus et al., 2018; Lam et al., 2012; Wei &

Kaushik, Friedman et al., 2015


Vikesland, 2015; Wei et al., 2015; Wu et al., 2014), Ag (Barud et al.,

Sun, Yang, Wang et al., 2010


2011; Diez et al., 2011; Dong et al., 2013; Fortunati et al., 2014; Hoeng

Gopiraman et al., 2015


et al., 2017; Hoeng et al., 2015; Liu et al., 2011; Lokanathan et al.,

Goswami & Das, 2018

Shin, Bae et al., 2007


Johnson et al., 2011
Benaissi et al., 2010

Hebeish et al., 2014


Bendi & Imae, 2013
2014; Ramaraju et al., 2015), Pd (Cirtiu et al., 2011), Pt (Johnson et al.,

Chetia et al., 2017


Xiang et al., 2018
Cirtiu et al., 2011

Dutta et al., 2018


Dong et al., 2018

Jiao et al., 2018


2011; Lin et al., 2011), Ru (Gopiraman et al., 2015; Kaushik, Friedman
Li et al., 2017

et al., 2015). Among them, Au nanoparticles (AuNPs) and Ag nano-


particles (AgNPs) are most studied. Physical deposition is a simple
process, generally achieved by electrostatic association (Dong, Yan,
Ref.

Ren, Zhang, & Lei, 2018; Kim, Ko, Kwon, Choo, & You, 2018; Lam et al.,
2012; Zhang et al., 2015). Negatively-charged carbonate-stabilized
Catalyst for the aza-Michael reaction of 1-phenylpiperazine with
Electrochemical biosensing of ascorbic acid, dopamine, and uric

AuNPs were effectively and evenly deposited on positively-charged


Catalyst for controlled and selective oxidation of sulfides and

Catalyst for azide-alkyne cycloaddition reaction in glycerol

poly (diallyldimethyl ammonium chloride)-functionalized NCC via


electrostatic interaction (Lam et al., 2012). AuNPs have also been
successfully loaded on NFC film (nanopaper) via vacuum filtration as
Recyclable dip-catalyst for Suzuki–Miyaura reaction

Electrocatalysis of the oxygen reduction reaction

well as direct dropping AuNP suspension on NFC layer (Kim et al.,


Recyclable catalysts for cross-coupling reaction
Catalyst for hydrogenation and Heck coupling

Catalyst for the nitroaromatic hydrogenation

2018; Zhang et al., 2015). The NFC-based matrix enables the direct
AuNP deposition by filtration due to its nanoscale surface roughness. In
addition, the filtration process allows for the precise control of the
Catalyst for hydrogenation of arenes

Catalyst for C-N coupling reactions

spatial distribution of AuNPs, including the number density and size


Catalyst for water denitrification

ratio, which are strongly associated with interparticle plasmon coupling


Enhanced radiation therapy

effect (Kim et al., 2018).


Compared to physical loading, in situ chemical deposition is more
Conductive textiles

favorable to realize the uniform distribution of nanoparticles on na-


nocellulose. The surface charge density of nanocellulose is a key factor
acrylonitrile
Application

for the electrostatic adsorption of noble metal ions and shows sig-
alcohols

nificant influence on the shape, morphology, and suspension stability of


acid

the resulting particles. For example, partially desulfated NCC is able to


stabilize the AgNPs better than the pristine NCC. The size distribution of
TEMPO-oxidized NFC

TEMPO-oxidized NFC

TEMPO-oxidized NFC

AgNPs is significantly improved as the extent of desulfation increases


(Lokanathan et al., 2014). Carboxylate groups available on the NCC
surface provide new sites for nucleation stage via electrostatic adsorp-
tion, so the size of nanoparticles is greatly dependent on the surface
Substrate

carboxyl number. At a high level of charge density of TEMPO-oxidized


NCC

NCC
NCC
NCC

NCC

NCC

NCC
NCC

NCC
BNC

BNC
NFC

NFC

NCC, carboxylate groups are present in sufficient quantity, allowing the


synthesis of smaller AgNPs on the entire NCC surface (Hoeng et al.,
PdCl2, CuCl2 / in situ reduction by potassium borohydride

2015).
Ni (NO3)2/ in situ thermal reduction process under N2)

In addition, reductants are generally required to induce the metal


precursor nucleation of in situ deposition and control the morphology of
CuSO4/ in situ reduction by hydrazine hydrate

CuSO4/ in situ reduction by hydrazine hydrate

the metal nanoparticles on nanocellulose, such as borohydride


Cu(OCOCH3)2 / in situ reduction by NaBH4

(Lokanathan et al., 2014), ascorbic acid (Eisa et al., 2018), trisodium


CuCl2/ in situ reduction by ascorbic acid
RuCl3/ in situ reduction by H2 pressure
PdCl2/ in situ reduction by dihydrogen

Bi(NO3)3 / in situ reduction by NaBH4

citrate(Na3Cit) (Nabeela et al., 2016), glucose (Wang et al., 2016),


K2PdCl4/ in situ reduction by NaBH4

CuSO4/ in situ reduction by NaBH4


RuCl3/ in situ reduction by NaBH4
H2PtCl6/ in situ reduction by NCC
H2PtCl6/ in situ reduction by NCC

polydopamine (PDA) (Tang, Shi, Berry, & Tam, 2015), polyamidoamine


H2PtCl6/ electrostatic adsorption
PdCl2/ in situ reduction by PDA
Precursor and synthesis method

(PAMAM) (Chen, Cao, Quinlan, Berry, & Tam, 2015), etc. (Barud et al.,
2011; Jesus et al., 2018; Lam et al., 2012). AuNPs/BNC nanocomposites
were synthesized by boiling HAuCl4-treated BNC in Na3Cit solution to
produce AuNPs fully intercalated within the BNC network (Wei &
Vikesland, 2015). In a system using Na3Cit as a reduction and capping
agent, the synergistic effect of NFC and Na3Cit resulted in anisotropic
growth of flower-like Ag nanostructures (AgNF) (Nabeela et al., 2016).
NCC can also serve as the deposition substrate, allowing glucose to
reduce Tollen’s reagent to produce Ag NPs (Wang et al., 2016). Poly-
dopamine (Lee, Dellatore, Miller, & Messersmith, 2007; Ye, Wang,
Inorganic nanoparticles (size in nm)

Zhang, Zhou, & Liu, 2010), which contains both catechol and amine
groups, was coated on the surface of NCC as a secondary mediated
platform of reduction reaction. As a result, the nanocomposite posses-
PtNPs (2.00 ± 0.4 nm)
PdNPs (3.6 ± 0.8 nm)

sing a core-shell structure was obtained with numerous “satellites” of


RuNPs (3.3 ± 1 nm)
RuNPs (8 ± 2.0 nm)
Table 1 (continued)

Pd-Cu NPs (4.0 nm)

Ag NPs decorating the NCC surface. The XRD reflections of crystalline


CuNPs (14.65 nm)
Non-noble metal

CuNPs (7–25 nm)

NiNPs (5–12 nm)


BiNPs (2–10 nm)
PtNPs (∼21 nm)

CuNPs (6–7 nm)


CuNPs (5.1 nm)
PdNPs (2.5 nm)

structure from NCC@PDA exhibited almost no differences except for a


PtNPs(4.3 nm)

CuNPs (7 nm)

slight reduction in the intensity, confirming that coated PDA did not
destroy the crystal structures of cellulose (Tang et al., 2015). Similarly,
PdNPs

spherical Pd NPs with a narrow size distribution were uniformly dis-


persed on the surface of NFC via in situ growth in the presence of PDA

4
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Table 2
The synthesis methods and applications of nanocarbons/nanocellulose composites.
Inorganic nanoparticles (size in nm) Precursor and synthesis Substrate Application Ref.
method

Nanocarbons
CQDs (10 nm) Combination via NHS/EDC TEMPO-oxidized NCC Bioimaging Guo et al., 2017
reaction
S, N codoped GQDs (3.52 ± 0.5 nm) Combination via NHS/EDC TEMPO-oxidized NCC Photoluminescent sensor Ruiz-Palomero, Soriano
reaction et al., 2017
CQDs (10-30 nm) Combination via NHS/EDC carboxymethylated NFC – Junka et al., 2014
reaction
GQDs (average diameter of 12.8 ± 0.9 nm and Combination via NHS/EDC NCCs Injectable fluorescent material in 3D Khabibullin et al., 2017
height of nd 0.250 ± 0.021 nm) reaction printing
CQDs (6-11 nm) Combination via NHS/EDC TEMPO-oxidized NCC Photoluminescent hybrid film Jiang et al., 2016
reaction
GQDs (3.5 ± 0.5 nm) Combination via NHS/EDC TEMPO-oxidized NFC Fluorescent detection of laccase Ruiz-Palomero, Benitez-
reaction Martinez et al., 2017
CNTs (average bilayer thickness of 17 nm) Self-assembly NCC – Olivier et al., 2012
CNTs Electrostatic adsorption NCC Conducting materials Farjana et al., 2013
CNTs Electrostatic adsorption BNC Biological fuel cell Lv et al., 2016
CNTs (15–20 nm) Electrostatic adsorption BNC Conducting materials Yoon et al., 2006
CNTs (1.5, 1.7 and 3.9 nm) Electrostatic stabilization NCC Conducting materials Hajian et al., 2017
CNTs Foam forming process NFC Conducting materials Siljander et al., 2019
graphene Electrostatic stabilization NCC Chemical sensing of organic solvent Cao et al., 2016
GO Electrostatic stabilization TEMPO-oxidized NFC Conducting materials Li et al., 2014
GO (7.0–15.1 nm per bilayer) Electrostatic stabilization NCC Conducting materials Xiong et al., 2016
GO Incorporation during the BNC Flexible supercapacitors Jiang et al., 2017
growth of BNC
GO Layer-by-layer assembly NFC Thermal conduction Song et al., 2017
GO Electrostatic stabilization NFC Supercapacitor Wang et al., 2017
GO In situ embedment NCC Enzyme immobilization Asmat & Husain, 2018
GO Electrostatic stabilization NFC Conducting materials Phiri et al., 2018
MnO2 /GO Freeze-drying process NFC Supercapacitors Zheng et al., 2018
GO (1 nm) Self-assembly TEMPO-oxidized NFC – Zhu et al., 2018
graphene (< 10 nm) Filtration NCC Thermally and electrically conductive Wang et al., 2015
flexible composite paper
graphene Assembly by diblock NFC Biomimetic nanocomposites Laaksonen et al., 2011
binding protein

(Li et al., 2017). Chen et al. first bonded Generation 6 polyamidoamine first dispersed in the aqueous suspension of TEMPO-oxidized NFC
or dendrimer onto the surface of oxidized NCCs (NCC-COOH) via amide (TONFC–COONa) and then left on the NFC by filtration into a film
bond, and then used the NCC-PAMAM hybrids with abundant metal- (Bendi & Imae, 2013). In order to improve the distribution uniformity
bound NH2 groups as carrier and reductant to prepare AuNPs (see of nanoparticles on nanocellulose, surfactants are usually used. Cetyl
Fig. 2) (Chen et al., 2015). Besides external reductants, nanocellulose trimethyl ammonium bromide (CTAB) was reported to be able to attract
itself has also been used as both reductant and supporter to syntheisze the copper ions and form micelles at high concentrations. The electron
and load metal nanoparticles via in situ synthesis (Drogat et al., 2011; rich activated hydroxyl groups on the surface of NCC could stabilize the
Xiong, Lu, Zhang, Zhou, & Zhang, 2013; Zhang et al., 2018). For ex- positively charged micelles by electrostatic action, leading to improved
ample, spherical PtNPs with the size of about 21 nm were successfully in dispersion of CuNPs without agglomeration (Goswami & Das, 2018).
situ synthesized on cotton NCC with hydroxyl groups (Xiong et al., Bi3+, which can bind to oxygen moieties on the surfaces or interstitial
2013). 2, 3-dialdehyde NFC was reported as both reducing and stabi- spaces of NFC, was reduced by sodium borohydride (NaBH4) to Bi na-
lizing agents to load Pb nanoparticles (PdNPs) and AuNPs, respectively noparticles within the interstitial spaces between the nanofibers (Jiao
(Zhang et al., 2018). Huang et al. reported that Ag+ could be reduced to et al., 2018). Ni nanoparticles were simply loaded on NCC via an in situ
Ag seeds by hydroxyl groups on the surface of NFC and the Ag seeds thermal reduction process without additional reducing agents. Hy-
could continuously grow with the addition of sodium citrate. The re- droxyl groups on the NCC are able to anchore and stabilize Ni(II) ions.
sults showed that the growth of the AgNPs was inhibited by nano- At 500 °C, Ni2+ was reduced to Ni nanoparticles with the size of
cellulose and affected by the concentration of Ag+; and meanwhile the 5–12 nm by the electrons released from the carbonized NCC (Shin, Bae
growth mode was changed from branch to bulk (Huang et al., 2019). et al., 2007).
Realizing high dispersibility and uniformity of metal nanoparticles on
nanocellulose is still a challenge for in situ method. It is necessary to
2.2. Nanocarbons
precisely control the experimental systems and parameters, such as
solvent, noble metal precursor (Xiong et al., 2013), pH, reaction time
Nanocarbons have excellent electrical and thermal conductivity
(Padalkar et al., 2010) and temperature (Chen et al., 2015), etc.
properties. However, they are difficult to be processed into a free-
standing material or a substrate due to the problem of aggregation. As
2.1.2. Non-noble metal nanoparticles an excellent supporter and stabilizer, nanocellulose has been combined
As a good biotemplate/skeleton, nanocellulose has also been used to with various nanocarbons including carbon quantum dots (Abbasi-
immobilize non-noble metal nanoparticles including Cu (Bendi & Imae, Moayed, Golmohammadi, & Hormozi-Nezhad, 2018; Guo et al., 2017;
2013; Chetia, Ali, Bordoloi, & Sarma, 2017; Dutta et al., 2018; Goswami Jiang, Zhao, Feng, Fang, & Shi, 2016; Junka, Guo, Filpponen, Laine, &
& Das, 2018; Hebeish, Farag, Sharaf, & Shaheen, 2014), Ni (Shin, Bae Rojas, 2014; Khabibullin et al., 2017; Ruiz-Palomero, Soriano, Benítez-
et al., 2007), and Bi (Jiao et al., 2018). Physical adsorption is a widely Martínez, & Valcárcel, 2017; Wu, Zhu, Dufresne, & Lin, 2019), carbon
adopted approach to conduct the deposition. For example, CuNPs were nanotubes (Farjana et al., 2013; Hajian, Lindstrom, Pettersson, Hamedi,

5
Q. Zhang, et al.

Table 3
The synthesis methods and applications of oxides nanoparticles/nanocellulose composites.
Inorganic nanoparticles (size in nm) Precursor and synthesis method Substrate Application Ref.

Oxides
SiO2 (∼23 nm) Template-assisted sol–gel route BNC – Wan et al., 2015
SiO2 (88–126 nm) Sol–gel route followed by vacuum drying NFC Superoleophilic substrate Le et al., 2016
SiO2 (100–1000 nm to 10–60 nm) Complexing and filtration NFC Composites with controlled pore structure and high surface Garusinghe et al., 2017
area
Fe3O4NPs (10–20 nm) / AuNPs (3–7 nm) Coprecipitation of FeCl3 and FeCl2; HAuCl4/ in situ reduction by NCC Enzyme immobilization Mahmoud et al., 2013
NaBH4
Fe3O4NPs Coprecipitation of Fe3(NO3)3 and FeSO4 NCC Drug removal Chen et al., 2014
Fe3O4NPs (< 100 nm) Coprecipitation of FeCl2 and FeCl3 BNC Magnetic nanohybrid Zheng et al., 2013
Fe3O4 NPs (< 20 nm) Coprecipitation-cross-linking process NCC Enzyme immobilization and catalytic synthesis of dipeptide Cao et al., 2015
Fe3O4NPs (20 nm) Physical blending and filtration NFC Magnetic materials Li et al., 2013
TiO2NPs Vacuum-assisted filtration NCC Separation of oil/water emulsion and self-cleaning membrane Zhan et al., 2018
TiO2 (7 nm) Atomic layer deposition NFC Absorption of nonpolar liquids and oils Korhonen et al., 2011
TiO2NPs LBL electrostatic assembly and sol– gel route NCC – Nelson & Deng, 2006
TiO2NPs (3 nm) Sol–gel process NCC Photocatalytic degradation of methyl orange Liu, Tao et al., 2012
TiO2NPs In situ hydrolysis of TiOSO4 BNC Photocatalytic removal of methylene blue Brandes et al., 2018

6
TiO2NPs (7.2 nm) In situ hydrolysis of Ti(OBu)4 BNC Photocatalytic degradation of methyl orange Sun, Yang, Wang et al., 2010
TiO2NPs (7 nm) Chemical vapor deposition NFC Photoswitchable water absorption Kettunen et al., 2011
TiO2NPs Electrostatic adsorption NFC Antibacterial materials Missoum et al., 2014
ZnO-Ag NPs (9–35 nm) Zn(AcO)2, AgNO3/ in situ precipitation NCC Antibacterial materials Azizi et al., 2013
ZnO NPs (10–30 nm) Self-assembly NFC Antibacterial materials Zhao et al., 2017
ZnO NPs (40.7 nm ± 14.5 nm) Electrostatic assembly NFC Antibacterial materials Martins et al., 2013
ZnO NPs In situ plasma discharge process BNC Antibacterial materials Janpetch et al., 2016
ZnO NPs (30 nm) Electrostatic adsorption and ultrasound irradiation BNC Antibacterial materials Jebel & Almasi, 2016
ZnO NPs incorporated GO Zn(CH3COOH)2, graphene powder/Sol-gel method NCC Photocatalytic degradation of ciprofloxacin hydrochloride Anirudhan & Deepa, 2017.
MgO NPs In-situ wet chemical and the sonochemical methods BNC Antibacterial materials Mirtalebi et al., 2019
Cu2O NPs (36–60 nm) CuSO4/ in situ reduction by NFC NFC – Sabbaghan & Argyropoulos, 2018
CuO NPs (40 nm) Electrostatic adsorption BNC Antibacterial materials Almasi et al., 2018
CuO NPs In-situ sonochemical and precipitation methods BNC Antibacterial materials Almasi et al., 2019
SnO2 SnCl2 and triethanolamine /filtration BNC Electrochemical detection of nickel-ion Sakwises et al., 2017
MnO2 (500–1000 nm) Solution dip and electrodeposited process NFC Supercapacitors Gui et al., 2013
Al2O3 (∼17 nm)
Bi2O3 NPs Bi(NO3)3/layer-by-layer assembly TEMPO-oxidized NFC Treatment of wastewater Xiong et al., 2018
Fe2O3 (15–25 nm) Chemical co-precipitation and hydrogen-bonding interactions BNC Flexible magnetic paper Barud et al., 2015
MnFe2O4/ CoFe2O4 (∼150 nm) In situ hydrolysis NFC Magnetic membranes of loudspeaker Galland et al., 2013
CoFe2O4 (40-120 nm) FeSO4,CoCl2/Impregnation and thermal reaction BNC Magnetic materials Olsson et al., 2010
Carbohydrate Polymers 229 (2020) 115454
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Table 4
The synthesis methods and applications of other inorganic nanoparticles/nanocellulose composites.
Inorganic nanoparticles (size in Precursor and synthesis method Substrate Application Ref.
nm)

Mineral salts
ACCNPs (11.3 ± 0.5 nm) Calcium chloride hexahydrate/Physical blending NCC Flame retardants Gebauer et al., 2011
CaCO3 CaCl2, Na2CO3/in situ deposition assisted by BNC – Stoica-Guzun et al.,
ultrasonic irradiation 2012
Ca-P Biomineralization followed by incorporating BNC Bone-defect repair Hu et al., 2016
cellulase enzymes
Ca-P (∼30 nm) Biomineralization BNC – Wan et al., 2009
Ca-P (100 nm) Biomineralization BNC – Gao et al., 2010
HAp (NH4)2HPO4 and Ca(NO3)2/hydrogelation NFC Fire resistance Guo et al., 2018
followed by freeze-drying process
phenyl bis-phosphinato bismuth BiPh3 and Bi(OtBu)3/filtration NFC Antibacterial activity Werrett et al., 2018
BaTiO3(< 50 nm) Electrostatic adsorption Carboxymethylated NFC – Choi & Jeong, 2019
Quantum dots
CdS NPs (30–50 nm) CdCl2 and thiourea /hydrothermal process BNC Photocatalysis for methyl orange Yang et al., 2011
degradation
CdS NPs (30 nm) Cd(NO3)2 and Na2S/in situ synthesis BNC – Li et al., 2009
CdS NPs CdCl2 and Na2S/in situ synthesis TEMPO-oxidized NFC Photoelectric ink Tang et al., 2016
CdTe NPs Stabilization by hydrogen bonding TEMPO-oxidized NFC Fluorescent microspheres Guan et al., 2018
ZnSe NPs (5 nm) Suction filtration NFC Photoluminescent paper Xue et al., 2015
ZnS, CdS (5 nm) Adsorption NCC Semiconductor nanocomposites Hassan et al., 2010
Nonmetallic elements
SiNPs (≈100 nm) Adsorption BNC Conducting materials Park et al., 2016
SiNPs (≈50 nm) Vacuum-assisted filtration and covalent cross- NFC Electrode for flexible lithium-ion Zhou et al., 2018
linking effect batteries
SeNPs (10–20 nm) Na2SeO3 / in situ reduction by NCC NCC – Shin, Blackwood et al.,
2007
graphene (8 nm) and MoS2 Van der Waals interaction NFC Paper-based electronics and Bao et al., 2014
biosensors
Montmorillonite Physical blending and drying TEMPO-oxidized NFC Ultrastrong and high gas-barrier Wu et al., 2012
composites
Montmorillonite Physical blending and freeze drying NFC – Gawryla et al., 2009
Montmorillonite Soak adsorption and freeze drying BNC Wound dressing Ul-Islam et al., 2013

& Wagberg, 2017; Lv et al., 2016; Olivier et al., 2012; Yoon, Jin, Kook, making them natural partners in composite materials (Farjana et al.,
& Pyun, 2006), and graphene-related materials (Asmat & Husain, 2018; 2013; Hajian et al., 2017; Lv et al., 2016; Olivier et al., 2012; Yoon
Cao, Zhang, Wu, Wang, & Lu, 2016; Jiang et al., 2017; Phiri, Johansson, et al., 2006). Olivier et al. used single-walled carbon nanotube (SWNT)/
Gane, & Maloney, 2018; Song et al., 2017; Wang et al., 2017; Xiong NCC dispersions obtained by ultrasonication to create multilayered thin
et al., 2016; Zheng et al., 2018; Zhu, Monti, & Mathew, 2018) to fab- films via layer-by-layer (L-b-L) assembly using polyallylamine hydro-
ricate functional nanocomposites. chloride as a polyelectrolyte (Fig. 3). The short-range hydrophobic in-
teractions between the SWNTs and specific crystalline faces of the NCC
2.2.1. Carbon quantum dots are responsible for this specific architecture. Although hydrophobic
Carbon quantum dots (CQDs) have become research hotspot re- interactions are the driving forces for the association mechanism be-
cently because they are fluorescent, nontoxic, and readily water-dis- tween SWNTs and NCC, the long-range electrostatic repulsion between
persible (Zhao & Zhu, 2018; Zhu et al., 2015). CQDs can be synthesized the NCC also plays an important role in the stabilization of the CNTs/
from graphene, cellulose or other materials under high temperature and NCC dispersion (Olivier et al., 2012). Without the chemical functiona-
pressure (Zheng, Ananthanarayanan, Luo, & Chen, 2015). CQDs are lization of CNTs or the use of surfactant, long-term stable colloidal
usually combined with nanocellulose by covalent bonds, for instance, dispersions of CNTs in aqueous media were achieved with the help of
amino-functionalized CQDs were conjugated to carboxlylated NCC via the association between the NCC and CNTs (Hajian et al., 2017). The
carbodiimide-assisted coupling chemistry (Guo et al., 2017; Jiang et al., charges on the NCC induce an electrostatic stabilization of the NCC/
2016; Ruiz-Palomero, Soriano et al., 2017). Similarly, carbox- CNTs complexes that prevents aggregation.
ymethylated NFC was used to covalently bind CQDs by the well-known The composites of nanocellulose and CNTs will become conductive
N-(3Dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride/N-hy- as long as there are a sufficient number of junctions between the dis-
droxysuccinimide (EDC/NHS) coupling system (Junka et al., 2014; persed CNTs. Farjana et al. prepared conductive BNC films by treating
Khabibullin et al., 2017). CQDs/nanocellulose composites are mainly BNC with a dispersion of double-walled carbon nanotubes (DWCNTs)
made into the forms of membrane, paper, hydrogel and aerogel and multi-walled carbon nanotubes (MWCNTs) in the presence of CTAB
(Abbasi-Moayed et al., 2018; Jiang et al., 2016; Wu et al., 2019). Wu as a surfactant. A large number of small holes on the surface of BNC
et al. prepared CQDs/NFC fluorescent aerogels via secondary freeze- prevented the CNTs from entering the inside, thus forming a conductive
drying. NFC was first freeze-dried into an aerogel, and then covalently layer on the surface of the BNC (Farjana et al., 2013). Lv et al. fabri-
cross-linked with CQDs-reverse NHS/EDC in CQDs suspension as a cated electrically conducting composite membranes by incorporating
natural backbone. After re-lyophilization, a high CQD-loaded fluor- carboxylic multiwalled carbon nanotubes (c-MWCNTs) into BNC pelli-
escent aerogel was obtained (Wu et al., 2019). cles. The 3D BNC network provided a large surface area for the abun-
dant loading of c-MWCNTs (Lv et al., 2016).
2.2.2. Carbon nanotubes
Carbon nanotubes (CNTs) have excellent mechanical strength, high 2.2.3. Graphene and graphene oxide
electrical and thermal conductivities, high stability, and high aspect Graphene-related materials including graphene and graphene oxide
ratios. CNTs and nanocellulose have good affinity with each other, (GO) possess extraordinary electronic transport properties and high

7
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 2. (A) Schematic illustration of the NCC-PAMAM-Au synthetic process. The blue spheres represent PAMAM dendrimers, while the yellow and purple spheres
signify small and large gold nanoparticles, respectively; TEM images of (B) NCC-PAMAM-Au-1, (C) NCC-PAMAM-Au-2. (Modified from Chen et al., 2015 with
permission from American Chemical Society). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)

electrocatalytic activities. The nanocomposites composed of nano- porous network framework, in which GO nanosheets were uniformly
cellulose and graphene-related materials have shown the versatility and dispersed and fixed. The resulting composite can be used as a novel
broad application prospects in many fields (Asmat & Husain, 2018; Cao lipase nanobiocatalyst (Asmat & Husain, 2018). Jiang et al. introduced
et al., 2016; Jiang et al., 2017; Li et al., 2014; Phiri et al., 2018; Song a novel strategy for the fabrication of flexible, light-weight BNC-based
et al., 2017; Wang et al., 2017; Xiong et al., 2016; Zheng et al., 2018; electrodes involving the in situ incorporation of GO into a BNC matrix
Zhu et al., 2018). NCC and graphene nanoplatelets have been made into during its growth under aerobic and static growth conditions. GO flakes
electrically and thermally conductive hybrid thin films by simply fil- was interlocked within the nanocellulose network during BNC growth,
tration. Graphene nanoplatelets were well aligned within the hybrid enabling facile chemical reduction of GO sheets. The synthesis strategy
films, and a higher degree of alignment was induced by the hot-pressing prevented their restacking and loss of active area and led to excellent
process (Wang, Drzal, Qin, & Huang, 2015). A nanocomposite mem- energy storage performance as well as mechanical flexibility (Jiang
brane for Cu(II)-ion adsorption was successfully obtained based on the et al., 2017).
self-assembly of TEMPO-mediated oxidized cellulose nanofibers
(TONFC) and GO in high-porosity bio mixtures. Atomic force micro- 2.3. Oxides
scopy (AFM) confirmed that the GO nanoparticles first adhered and
then aggregated along a single TONFC fiber, meanwhile, the long and Nanocellulose as the supporter to load oxide nanoparticles, such as
flexible TONFC filaments were bound on a flat GO plane (Zhu et al., SiO2 (Garusinghe, Varanasi, Garnier, & Batchelor, 2017; Le et al., 2016;
2018). Besides membranes, other types of graphene/nanocellulose Wan, Yang, Xiong, Raman, & Luo, 2015), Fe3O4 (Chen, Berry, & Tam,
composites have also been reported. Laaksonen et al. successfully at- 2014; Li et al., 2013; Mahmoud, Lam, Hrapovic, & Luong, 2013; Zheng
tached graphene to NFC using genetically engineered hydrophobic et al., 2013), TiO2 (Brandes et al., 2018; Korhonen, Kettunen, Ras, &
proteins as diblock copolymer. The structure of the resulting gra- Ikkala, 2011; Liu, Tao, Bai, & Liu, 2012; Nelson & Deng, 2006; Sun,
phene@NFC composite resembled that of nacre where self-assembled, Yang, & Wang, 2010; Zhan et al., 2018), ZnO (Azizi, Ahmad, Hussein, &
aligned platelet-like aragonite reinforcements were embedded in a Ibrahim, 2013; Jebel & Almasi, 2016; Zhao, Zheng, Zou, Guo, & Pan,
protein matrix containing nanofibrillar chitin (Laaksonen et al., 2011). 2017), Cu2O (Sabbaghan & Argyropoulos, 2018), CuO (Almasi,
Asmat et al. prepared a NCC-polyvinyl alcohol (PVA) composite with Jafarzadeh, & Mehryar, 2018; Almasi, Mehryar, & Ghadertaj, 2019),

8
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 3. (A) Monoclinic unit cell and schematic cross-section of cellulose nanocrystals. The (200) and (2¯00) faces exhibit a higher hydrophobicity because of the
exposure of CH moieties and are preferential sites for interaction with hydrophobic SWNTs; (B) Representation of a 6.5 SWNT near the (200) hydrophobic plane of a
NCC; (C) AFM height image obtained in water for an SWNT/CN complex and its associated height profile along the blue line. The full-color Z scale corresponds to
15 nm; (D) TEM images of SWNT/NCC morphology from a negatively stained diluted dispersion. Short, thick objects are indicated by stars, and thinner, longer
objects are indicated by arrows; (E) SWNT/CN dispersions are used to create multilayered thin films with the layer-by-layer method using polyallylamine hydro-
chloride as a polyelectrolyte. (Modified from Olivier et al., 2012 with permission from American Chemical Society). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

MgO (Mirtalebi, Almasi, & Khaledabad, 2019), SnO2 (Sakwises, the work reported by Brandes et al., spherical BNC/TiO2 nanocompo-
Rodthongkum, & Ummartyotin, 2017), MnO2 (Gui et al., 2013; Zheng sites were produced by both ex situ and in situ methods through the
et al., 2018), and Bi2O3 (Xiong et al., 2018), has been extensively ex- interaction and entanglement of TiO2 NPs on the matrix of BNC
plored. The composites of oxide-nanoparticles and nanocellulose are (Brandes et al., 2018). In addition, the arrays of directional anatase
usually fabricated by sol-gel (Nelson & Deng, 2006), layer self-assembly TiO2 NPs were implanted into BNC by molecular imprinting tech-
(Zhao et al., 2017), atomic layer deposition (Gebauer et al., 2011), and nology. The resulting BNC/TiO2 nanocomposites had a hollow structure
in situ synthesis (Zhan et al., 2018). The crystal structure, size, shape, consisting of partially cemented anatase TiO2 with diameters in the
and the distribution of oxide nanoparticles are greatly dependent on the range of 4.3–8.5 nm (Sun, Yang, Wang et al., 2010).
morphology and surface functional groups of nanocellulose (Oun, Other common oxide nanoparticles, such as ZnO (Azizi et al., 2013;
Shankar, & Rhim, 2019). BNC has been used as the template and cat- Jebel & Almasi, 2016; Zhao et al., 2017), Cu2O (Sabbaghan &
alyst to fabricate the free-standing SiO2 nanotubes with 3D mesoporous Argyropoulos, 2018), CuO (Almasi et al., 2018, 2019), MgO (Mirtalebi
network structure. The high-density hydroxyl groups on the surface of et al., 2019), SnO2 (Sakwises et al., 2017), Bi2O3 (Xiong et al., 2018),
BNC are able to catalyze the hydrolysis and condensation of silica have also been reported to be loaded on nanocellulose. Zhao et al.
precursors to form silica nanoparticles at near-neutral pH under am- synthesized ZnO@NFC composites with hierarchical structure using an
bient conditions (Wan et al., 2015). Le et al. successfully prepared environmentally friendly hydrothermal method. ZnO nanoparticles
hydrophobic NFC-SiO2 film by a facile one-pot method using tetra- grew uniformly along the linear chain of NFC, and nanofiber compo-
ethoxysilane (TEOS) and dodecyl triethoxylsilane (DTES). DTES-mod- sites with linear array structure were obtained (Zhao et al., 2017).
ified spherical SiO2 nanoparticles with the particle sizes in the range of Sabbaghan and Argyropoulos (Sabbaghan & Argyropoulos, 2018) even
88–126 nm showed good self-assembly property on the NFC film (Le modulated alkaline reduction of Cu2+ ions aided by reducing the end
et al., 2016). As common but important nanomaterials, magnetic na- aldehyde groups of NFC to selectively deposit nano- and micro-sized
noparticles have been widely used to combine with nanocellulose for Cu2O cubes, truncated Cu2O cubes and Cu2O spheres in NFC gels. Since
the fabrication of novel magnetic nanocomposites (Barud et al., 2015; the reduction was provided solely by the chain end groups of NFC,
Chen et al., 2018; Galland et al., 2013; Mahmoud et al., 2013; Olsson supersaturation effect seemed to affect the Cu2O nucleation. At low
et al., 2010). Fe3O4 nanoparticles were deposited on the surface of BNC Cu2+ ion concentrations, the aldehyde end groups were immobilized on
by the coprecipitation of Fe(NO3)3/FeSO4 (2:1) in NaOH solution. the surface of NFC, creating Cu2O particles locally while their size re-
Herein, BNC served as a support matrix to control the loading of Fe3O4 mained small. Once, however, at critical Cu2+ ion concentrations, the
nanoparticles (Zheng et al., 2013). Berglund et al. immersed the tem- nucleated Cu2O sites were enough to be associated together to form a
plate of dried BNC aerogel into the aqueous FeSO4/CoCl2 solution, and uniform cubic configuration of larger dimensions (Fig. 4) (Sabbaghan &
successfully prepared the CoFe2O4@BNC composite aerogel with a Argyropoulos, 2018). Almasi et al. (Almasi et al., 2019) fabricated
porosity of about 99% using a coprecipitation method. The magnetic CuO/BNC nanohybrids by two in-situ syntheses including sonochemical
nanoparticles with a diameter of 40–120 nm were evenly dispersed on and precipitation methods. Sonochemical method is more effective than
the surface of BNC (Olsson et al., 2010). TiO2 is another widely studied precipitation method in the impregnation, and leads to more uniform
metal oxide nanoparticles loaded on nanocellulose. Zhan et al. (Zhan distribution of CuO nanoparticles (CuO NPs) inside the BNC matrix.
et al., 2018) synthesized UV-induced self-cleanable TiO2@TNCC Uniformly-distributed CuO NPs penetrated to inner spaces of BNC
membranes by in situ generation of TiO2 nanoparticles (TiO2 NPs) on membrane in the in-situ synthesized nanohybrids but the ready-
tunicate cellulose nanocrystals (TNCC) via the hydrolysis of TiOSO4. In purchsed CuO NPs agglomerated on the surface of ex-situ synthesized

9
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 4. (A) Reactions operating at reducing end groups of cellu-


lose or other carbohydrates. (B) Bar plots and associated scanning
electron photomicrographs showing the Cu2O particle develop-
ment as a function of increasing amounts of Cu2+ (S1 to S3) and
as a function of increasing amounts of added aldehyde end groups
in the form of added dextrose (SD1 to SD3). (Modified from
Sabbaghan & Argyropoulos, 2018 with permission from Elsevier).

nanohybrid. In sonochemical method, the ultrasonic-assisted fabrica- natural HAp in bones and teeth (Wan et al., 2009). Similarly, Gao et al.
tion of CuO/BNC nanohybrid was able to control the release rate of CuO used BNC as a template to simulate collagen nanofibers and deposit Ca-
NPs by increasing the entanglement intensity and decreasing CuO NPs P by biomineralization. The formed BNC/HAp composite possessed
size. Similarly, MgO nanoparticles were loaded on BNC via above two nano-scale structural units similar to biological bones (Gao et al.,
in-situ methods. The sonication during the in-situ synthesis decreased 2010). Hu et al. used an improved approach to prepare a bioabsorbable
the degree of nanocellulose crystallinity. In addition, the sonication was BNC composite that could achieve more Ca-P formed or deposited on
favorable for MgO nanoparticles to penetrate the precursors to the inner BNC in saturated simulated body fluids (SBF) (1.0×) with additional
space of BC network, leading to the disruption of the crystalline regions HAp nanopowder than that in oversaturated SBF (1.5×). (Binding Ca-P
of cellulose (Mirtalebi et al., 2019). Xiong et al. used the 3D multistage to BNC involves three processes). The mechanism of apatite crystal
framework constructed by the self-crosslinking of polyhydric NFC as a formation and bound to BNC contained three phase. Thereinto, the
matrix for the immobilization of titanate/Bi2O3 nanoparticles. The NFC formation of apatite crystal layer by the aggregation of HAp nuclei,
matrix optimized the inherent defects of loaded functional particles and induced by the dipole interaction between hydroxyl groups on the
greatly improved their ability of recapturing nocuous cations and an- surface of BNC and Ca2+, is the first key step for the loading of HAp on
ions (Xiong et al., 2018). SnO2, which is commonly employed in pho- BNC. Freeze-drying is a useful method to prepare porous composites of
tocatalysis and gas detection, has been combined with BNC to obtian nanocellulose and mineral salts, such as foam and aerogel (Hu et al.,
SnO2/BNC composites by simply mixing SnO2 with BNC suspension and 2016). Guo et al. prepared NFC/HAp composite foam by a simple
filtering the mixture into a paper. The intercalated structure of SnO2 freeze-drying process, in which HAp nanofibers with diameters of about
within BNC networks solved the usage restriction brought by its powder 20 nm were combined with NFC through a crosslinking agent. The re-
form, stiffness and brittleness (Sakwises et al., 2017). sulting composite foam had a well-defined porous structure with pore
sizes ranging from several micrometers to several hundred micro-
2.4. Mineral salts meters, and could be used as an insulating and flame-retardant building
material (Guo et al., 2018).
Various mineral salts, including calcium carbonate (CaCO3) In addition to calcium salt, phosphinato bismuth(III) complexes
(Gebauer et al., 2011; Stoica-Guzun et al., 2012), calcium phosphate ([BiPh(OP(=O)R1R2) (R1=Ph, R2=H; R1=R2=Me)]), derived from
(Ca-P) (Hu et al., 2016; Zhang et al., 2009), calcium hydroxyphosphate the treatment of phosphinic acids with either Bi(OtBu)3 or BiPh3, were
(HAp) (Guo et al., 2018, Gao et al., 2010; Wan et al., 2009), bismuth incorporated into NFC to generate bismuth-impregnated paper com-
salt (Werrett et al., 2018) and barium titanate (BaTiO3) (Choi & Jeong, posites (Werrett et al., 2018). Choi and Jeong fabricated eco-friendly
2019), have been combined with nanocellulose to prepare composites piezoelectric composite films using lead-free BaTiO3 nanoparticles and
with designed architecture and improved biocompatibility (Torres, NFC via an facile aqueous suspension casting. The composite film
Commeaux, & Troncoso, 2012). Calcium chloride (CaCl2) and sodium possessed the maximum piezoelectric properties with 60% BaTiO3
carbonate (Na2CO3) have been used as starting reactants to synthesis content, above which the mechanical stiffness would decrease (Choi &
and deposit CaCO3 on nanocellulose (Stoica-Guzun et al., 2012). Ge- Jeong, 2019). Montmorillonite/NFC composite aerogels with proper
bauer added CaCl2 to the NCC suspension and used ethanol as a dis- mechanical properties were obtained via freeze-drying. The lyophili-
persant to prepare optically transparent and high-strength nano- zation process promoted the formation of a three-dimensional network
composite of amorphous calcium carbonate nanoparticles (ACCNPs)/ with nanoscale “wattle-and-daub’’ structure consisting of mud-like
NCC in an ultrasonic bath. The uniformity and anisotropy of nano- montmorillonite and straw-like NCC (Gawryla, van den Berg, Weder, &
composite can be tuned by controlling the interaction between NCC and Schiraldi, 2009).
ACCNPs (Gebauer et al., 2011). Phosphorylated BNC is used as nano-
template for the early mineralization of Ca-P in order to further un- 2.5. Quantum dots
derstand the early deposition mechanism of HAp on nano-substrates.
The platelet-like Ca-P coating deposited onto BNC was analogous to Quantum dots (QDs) are semiconductor nanocrystals with unique

10
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

performance including high fluorescence intensity, good optical stabi- 2014; Lopes, Sanchez-Martinez, Stromme, & Ferraz, 2017). Because of
lity and tunable emission wavelength. With nanocellulose as the carrier low toxicity and good biocompatibility, the nanocellulose matrix allows
of QDs, the synthesized hybrid nanocomposites, have found applica- numerous applications related to antibacterial and biomedical mate-
tions in bioimaging, biotoxicity studies, sensing devices, and optical rials after being incorporated with antibacterial nanoparticles, such as
components (Chen, Lai, Marchewka, Berry, & Tam, 2016; Liu & Luo, Ag, ZnO and TiO2. NCC loaded with AgNPs has been widely used as
2014; Tang et al., 2016). Transparent and photoluminescent NFC paper antibacterial materials (Drogat et al., 2011; Singla et al., 2017). Drogat
loaded with high-quantum-yield ZnSe QDs has been reported via simple et al. reported AgNPs/NCC composites with a broad antibacterial ac-
suction filtration. The ZnSe QDs with good dimensional stability can be tivity against both Gram-negative Escherichia coli (E. coli) and Gram-
well dispersed in the NFC matrix without aggregation (Xue, Song, Yin, positive Staphylococcus aureus (S. aureus). With the combination of
Wang, & Wang, 2015). Guan et al. prepared fluorescent CdTe-QDs-en- antibacterial activity, biocompatibility and water-absorption ability,
coded NFC microspheres by mechanical spraying, freeze-molding and the AgNPs/NCC nano-biocomposites could further act on skin repair
subsequent electrostatic cross-linking by calcium ion. CdTe QDs were and have synergistic effect on wound healing in vivo (Drogat et al.,
efficiently and homogeneously fixed in the network of intertwined NFC, 2011). When NCC/AgNPs was added as a functional filler into other
driven by hydrogen bonding (Guan et al., 2018). Hassan successfully substrates, in addition to the introduction of antibacterial properties,
loaded ZnS and CdS quantum dots with uniform diameter of 5 nm by the mechanical and thermal properties of the matrix were also im-
impregnation adsorption using NFC obtained from bleached bagasse as proved due to the presence of NCC (Fortunati, Armentano, Zhou,
template (Hassan, Ward, & Eid, 2010). Iannoni et al., 2012; Fortunati, Armentano, Zhou, Puglia et al., 2012;
Besides physical loading, QDs could also be synthesized and de- Liu, Song, Shang, Song, & Wang, 2012). Fortunati et al. developed a
posited in situ on different types of nanocellulose (Li et al., 2009; Tang poly(lactic acid) (PLA) film combined with surfactant-modified AgNPs/
et al., 2016). When using carboxylated NFC as the template for the NCC as the biocides. The presence of the NCC addressed the slow
loading of CdS QDs, the molar ratio of Cd2+/COOH was found of great crystallization of PLA and imparted the PLA matrix with high me-
significance. The average size of CdS/NFC nanocomposites was tripled chanical and good thermal properties in both binary and ternary sys-
as the molar ratio of Cd2+/COOH increased from 0.3 to 2 (Gao et al., tems (Fortunati, Armentano, Zhou, Iannoni et al., 2012; Fortunati,
2010). Yang et al. reported a simple and effective hydrothermal reac- Armentano, Zhou, Puglia et al., 2012).
tion to deposit CdS QDs on hydrated BNC. The coordination effect be- Compared with NCC, the larger aspect ratios of NFC are more fa-
tween CdS QDs and the hydroxyl groups of cellulose is beneficial to vored by the formation of entanglement networks, which is more
stabilizing the CdS QDs on BNC (Yang et al., 2011). Chemical coupling conducive for the loading of antibacterial nanoparticles. Different forms
is another approach to combine QDs with nanocellulose. QDs with PEG- of AgNPs/NFC composites, e.g., paper (Martins et al., 2012), film, hy-
amine surface ligands were successfully conjugated to carboxylated drogel and aerogel (De France, Hoare, & Cranston, 2017; Dong et al.,
NCC via an amide linkage. The results from fluorescenct spectroscopy 2013), have been developed to present antibacterial properties. Besides
indicated reaction efficiency up to 20% (Abitbol et al., 2017). AgNPs, some other nanoparticles, such as ZnO (Martins et al., 2013)
and TiO2 (Missoum, Sadocco, Causio, Belgacem, & Bras, 2014; Xiao, Xu,
2.6. Nonmetallic elements Liu, Hu, & Huang, 2013), are also found of antibacterial property on
NFC. ZnO/NFC nanocomposite was used as functional filler in starch-
In addition to above mentioned nanomaterials, some uncommon based coating formulations, which endowed the coated paper sheets
nanoparticles on nanocellulose, such as silicon (Park, Lee, Shin, Kim, & with antibacterial activity accompanied by the improvements in their
Hyun, 2016; Zhou et al., 2018) and selenium nanoparticles (Shin, mechanical performance and air permeability (Martins et al., 2013).
Blackwood et al., 2007), have also been explored for the combination The functionalization of NFC with TiO2 nanoparticles generated a sy-
with nanocellulose. Park et al. prepared conductive PANi-Si-BNC nergistically antibacterial effect, significantly enhancing the anti-
composite using BNC as a template to bind Si nanoparticles (SiNPs) bacterial performance of the grafted NFC (Missoum et al., 2014). Xiao
along with in situ polymerization of 3D networked polyaniline (PANi). et al. developed a TiO2/chitosan/NFC composite via a layer-by-layer
In their work, phytic acid was added to introduce hydroxyl groups on process, followed by the deposition of AgNPs via UV irradiation. The
the surface of SiNPs, which enabled SiNPs to be uniformly attached on cable-like NFC composite exhibited extraordinary antibacterial activity
the surface of BNC pellicles along the nanofibers via hydrogen bonding against both Gram-positive and Gram-negative bacteria due to the
(Park et al., 2016). A lamellar graphene/nanocellulose/silicon (gra- coated TiO2, chitosan and AgNPs (Xiao et al., 2013).
phene/NFC/Si) film was assembled via a facile vacuum-assisted filtra- BNC is widely reported topical material for specific applications in
tion approach accompanied by the covalent cross-linking of glutar- bioengineering and biomedical fields owing to its intrinsic character-
aldehyde. SiNPs of 50–60 nm were confined in the network of graphene istics, such as high purity, crystallinity, water retention, high wet ten-
nanosheets and entangled NFC. The special composite structure con- sile strength and excellent biocompatibility owing to its“collagen-like”
tributed to the well dispersion of SiNPs as well as eliminated the re- component. The AgNPs/BNC composites, which were prepared by de-
stacking of graphene sheets (Zhou et al., 2018). Shin, Blackwood et al. positing AgNPs with a diameter of 16.5 nm on TEMPO-oxidized BNC
(2007) loaded Se nanoparticles (SeNPs) on the surface of NCC using pellicle, possessed high biocompatibility (cell viability > 95% after
NCC as both reducing and structure-directing agents. Either Na2SeO3 or 48 h of culture) and showed 100% and 99.2% antibacterial activity
H2SeO3 could be reduced to form elemental SeNPs with diameter of against E. coli and S. aureus, respectively (Fig. 5) (Wu, Fuh et al., 2018).
10–20 nm under hydrothermal conditions. Montmorillonite (MMT)/BNC composite films containing different
metal ions showed certain disinfecting activity and high mechanical
3. Applications of nanoparticle-loaded nanocellulose strength. The addition of Cu ions, compared to Na ions and Ca ions,
exceptionally enhanced the antibacterial property of the MMT/BNC
3.1. Antibacterial and biomedical materials composite film (Ul-Islam, Khan, Khattak, & Park, 2013). The ZnO-de-
posited BNC composites also demonstrated strong antibacterial activity
When it comes to biomedical applications, the toxicity and bio- against both E. coli and S. aureus bacteria. The bacterial inhibition zone
compatibility of nanocellulose have to be concerned, especially con- of both bacterial strains became broader with an increase in the ZnO
sidering the potential risks of the nanoscale, preparation method and content in ring diffusion test (Janpetch, Saito, & Rujiravanit, 2016).
modification. To date, nanocellulose has not been found to develop
cellular rejection and inflammation in vivo (Alexandrescu, Syverud,
Gatti, & Chinga-Carrasco, 2013; Kovacs et al., 2010; Lin & Dufresne,

11
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 5. (A) FE-SEM images of the TOBNCP/AgNP. The arrows indicate the in situ synthesized AgNP; (B) Growth inhibition zones of the TOBNCP/AgNP against (a) E.
coli and (b) S. aureus at 37 °C for 24 h; (C) Viabilities of (a) E. coli and (b) S. aureus incubated in the different pellicle extracts at 37 °C for 24 h. Note the different scales
of Y-axis in the figures. The value of the viability was written on each group. (Modified from Wu, Fuh et al., 2018; Wu, Song et al., 2018 with permission from
American Chemical Society).

3.2. Protein and DNA immobilization flavour compound) (Asmat & Husain, 2018).

Nanocellulose composites, which possess the advantages of reactive


3.3. Optical and electronic materials
surface groups and high specific surface area, are new platforms for the
immobilization of biomacromolecules. Nanocellulose loaded with metal
Nanocellulose itself is not a luminescent or conductive material.
nanoparticles has been extensively studied for such applications,
However, when properly loaded with specific nanoparticles, nano-
especially AuNPs and AgNPs (Lokanathan et al., 2013; Mahmoud, Male,
cellulose can have photoelectric and photothermal performance,
Hrapovic, & Luong, 2009). Cyclodextrin glycosyl transferase (CGTase)
leading to potential applications in fluorescent probes (Xue et al.,
and alcohol oxidase were reported to bind to activated AuNPs/NCC
2015), photothermal fillers (Hu, Meng, Liu, Fu, & Lucia, 2017;
matrix. The catalytic platform showed excellent enzyme stability and
Toncheva et al., 2018), battery (Lv et al., 2016) and photoelectric ink
no significant loss of original activity. Meanwhile, the recovered spe-
(Tang et al., 2016). NCC has lower transparency and can be used as a
cific activities were ∼70% and 95% for CGTase and alcohol oxidase,
higher light scattering point source, that is, a scattering agent that en-
respectively. (Mahmoud et al., 2009) Glucose oxidase enzyme was
hances the photothermal effect in nanocomposites. By adding AuNPs/
conjugated on the AuNPs@NCC composites via carbodiimide coupling
NCC as a bifunctional nanofiller into poly(vinyl alcohol) (PVA) film, the
and subsequent activation of linker-carboxylic acid groups. The de-
composite film is rendered high mechanical strength and photothermal
position of AuNPs increased the specific surface area of NCC and im-
effect. AuNPs scattered incident light in the film and acted as a sec-
proved its chemical affinity. The enzyme immobilization loading was
ondary source of absorption, thus further improving the photothermal
affected by the length of the thiol-linked chains modified on the surface
efficiency (Fig. 6) (Hu et al., 2017). In addition, the light-triggered
of AuNPs (Incani, Danumah, & Boluk, 2013). Moreover, magnetic Fe3O4
shape memory nanocomposites were prepared by mixing AuNPs@NCC
nanoparticles has been loaded on NCC and used as the enzyme carrier
with polyurethane. The “nanorod-like” structures of AuNPs@NCC al-
for the immobilization of papain. The activity recovery of PA im-
lowed for a long-distance and strong coupling plasmonic effect between
mobilized on this magnetic NCC composite was 80.1% (10.9 U/mg
the AgNPs along the NCC axis, thus ensuring a fast photothermal shape-
support) (Cao, Xu, Li, Lou, & Zong, 2015). NCC carrier loaded with both
recovery effect upon IR light illumination.(Toncheva et al., 2018) Xue
Fe3O4 NPs and AuNPs was also used for the effective immobilization of
et al. fabricated a transparent and photoluminescent foldable NFC
papain and the separation of reaction mixtures (Mahmoud et al., 2013).
paper using a suction filtration method. The ZnSe QDs with a high
In addition, Asmat et al. reported that the Candida rugosa lipase could
quantum yield was incorporated as a functional filler and poly-
be immobilized onto polypyrrole (Ppy)/NCC/GO through physical ad-
ethylenimine (PEI) was added to improve the retention of ZnSe QDs in
sorption, leading to the enhanced catalytic performance as high as
the composite paper (Xue et al., 2015).
160% of activity yield in the synthesis of ethyl acetoacetate (fruit
Electronic nanocomposites based on nanocellulsoe substrate have

12
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 6. (A) Proposed mechanism for the influence of CNCs on the photothermal effect of AuNPs within the PVA films; (B) Temperature changes at steady-state of
PVA、AuNP/PVA and Au/CNC/PVA films; (C) Three-dimensional images of the temperature distribution on the surface of Au/CNC/PVA (4 wt %Au/CNC) films.
(Modified from Hu et al., 2017 with permission from American Chemical Society).

also been widely investigated. Conductive nanocomposites can be stability, separation ability and recyclability (Kaushik & Moores, 2016).
prepared by combining BNC with CNT. When BNC was treated with The widely reported nanoparticles deposited on nanocellulose for cat-
DWCNT, the highest conductivity reached 0.39 S cm−1; whereas alysis include Pd (Benaissi et al., 2010), Au (Lam et al., 2012), Pt
treated with MWCNT, the highest conductivity was further increased to (Johnson et al., 2011), ZnO (Anirudhan & Deepa, 2017), TiO2 (Sun,
1.6 S cm−1. The maximum strain coefficient of the highest conductivity Yang, Wang et al., 2010), and Ru (Gopiraman et al., 2015). Compared
sample treated by MWCNT was 252 (Farjana et al., 2013). Lv et al. to other heterogeneous catalysts, the catalytic efficiency of these na-
prepared electrically conducting composite membranes by in- nocomposites is close to that in the molecular level due to the nanoscale
corporating carboxylic multiwalled carbon nanotubes (c-MWCNTs) into dimensions.
BNC pellicles. Laccase and glucose oxidase were successfully im- The composites of PdNPs@NFC have shown significantly improved
mobilized onto BNC/c-MWCNTs composite membranes via physical catalytic activity and excellent recyclability in the coupling and re-
adsorption. The enzyme biological fuel cell (EBFC) based on BNC/c- duction reactions (Cirtiu et al., 2011; Li et al., 2017; Xiang, Chen, Liu, &
MWCNTs composite membranes exhibited excellent performance with Lu, 2018; Zhang et al., 2018). It was reported that the product yield of
the highest open circuit voltage (0.76 V) and a maximum power density the Suzuki coupling reaction between aryl bromides and phenyl boronic
value (55 u W/cm 3) (Lv et al., 2016). Siljander et al. adopted a foam acid was more than 90% after 1 h with 0.1 mol% PdNPs@NFC catalyst
forming process to prepare conductive non-woven CNT/NFC sheets, (Zhang et al., 2018). Xiang et al. prepared Pd@BNC nanocomposites by
where NFC acted as a carrier for CNT. The resulting non-woven sheets in situ reduction method and further combined them with bleached
allowed the better surfactant selection. With the aid of sonication bagasse pulp (BSBP) by papermaking process to prepare “dip-catalyst”.
process the foam formed from CNT/NFC dispersion achieved the even The “dip-catalyst” was easily manufactured, and had the good recovery
higher coverage of CNT over NFC networks, resulting in high con- ability and high catalytic efficiency in the Suzuki–Miyaura reaction.
ductivity of 7.7 S/m (Siljander et al., 2019). A new photoelectric ink BNC as a supporting component provided mechanical strength and
was prepared based on the NFC/CdS QD composites, in which the CdS improved the contact between the reactants and Pd particles due to the
QDs and the NFC acted as pigment and binder, respectively. The pho- high porosity (Xiang et al., 2018).
tocurrent of the composites reached as high as 2 μA by adjusting the Besides coupling reactions, nanocellulose loaded with nanoparticles
carboxylate content and the molar ratio of Cd2+/–COOH. The photo- has also been widely applied to the reduction and oxidation reactions
electric ink was stable with good fluidity and rheology, providing po- (An, Long, & Ni, 2017; Gopiraman et al., 2015; Lam et al., 2012; Tang
tential application in screen-printing and 3D printing (Tang et al., et al., 2015). The good dispersion and narrow distribution of nano-
2016). particles in the catalytic system contribute to the enhanced catalytic
performance (An et al., 2017). Tang et al reported a composite catalyst
3.4. Catalysis of PDA-coated NCC loaded with AgNPs (AgNPs/PDA/NCC) on reducing
4-nitrophenol to 4-aminophenol, and found that the reaction rate of
Recently, nanocellulose has been regarded as high-efficienct, cost- NCC@PDA-AgNPs was 6 times faster than that of pristine AgNPs. The
effective and degradable catalyst-supporting substrate. Using nano- activation energy determined from the Arrhenius relationship was
cellulose as support to load nano-structured catalyst can improve the 33.88 kJ/mol for the nanocatalyst, as shown Fig. 7 (Tang et al., 2015).

13
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 7. (A) Schematic illustration of the strategy for synthesis of NCC@PDA, and the possible mechanism of metallization of AgNPs, and binding with β-cyclodextrin;
TEM images of core−shell (B) NCC@PDA, at a weight ratio of 1:1, (C) NCC@PDA-AgNPs, and (D) pure AgNPs reduced by dopamine. (Modified from Tang et al.,
2015 with permission from American Chemical Society).

Similarly, PDDA-coated NCC loaded with AuNPs was used for reducing increased, leading to the reduction in the intensity of surface plasmon
4-nitrophenol to 4-aminophenol. The nanocomposite catalyst achieved resonance (LSPR) absorption spectra of the embedded AgNPs and a
an activation energy of 69.2 kJ mol−1 and the reaction rate constant k change in color from amber to light amber, which could even be vi-
was (5.1 ± 0.2) × 10−3 s−1 (Lam et al., 2012). RuNPs supported on sually determined (Heli, Morales-Narvaez, Golmohammadi, Ajji, &
NFC was reported to catalyze the oxidation of benzyl alcohol to ben- Merkoci, 2016). A low-cost fluorescent NFC hydrogel loaded with
zaldehyde at 120 °C for 24 h with 89% yields (Gopiraman et al., 2015). sulfur, nitrogen-codoped graphene quantum dots (GQDs) was applied in
These results proved superior to catalysis done by RuNPs supported the detection of laccase enzyme. On the fluorimetric platform, Laccase
onto titania or alumina. weakly interacted with the graphitic layers stabilized by NFC, leading
to the energy transfer, and consequently to the fluorescence quenching
of the GQDs. The detection limit (MDL) for Laccase with this method
3.5. Sensors
was 0.048 U mL−1 (Ruiz-Palomero, Benitez-Martinez et al., 2017).
Based on the fact that the production of AgNPs is sensitive to the
Nanocellulose is one of the excellent sensor substrates for a variety
glucose concentration and reaction temperature, the sensor based on
of sensing applications when combined with various types of functional
AgNPs/NCC composite has been developed for the high-sensitivity
nanomaterials, such as plasmonic nanoparticles, photoluminescent na-
analysis of serum glucose and the monitoring of glucose concentration
noparticles, conductive (nano)materials (Schlesinger, Giese, Blusch,
in culture medium during cell culture (Wang et al., 2016). Horseradish
Hamad, & MacLachlan, 2015). This type of nanocellulose composites is
peroxidase (HRP) biosensor for high-sensitivity and high-selectivity
able to detect target analytes via colorimetric assay, fluorescence,
detection of hydrogen peroxide has also been successfully fabricated by
electrochemical signal, and surface enhanced Raman scattering spec-
simply inserting HRP into the nano-network structure of Au-BNC na-
troscopy (SERS). For example, AgNPs/BNC was used as a chemical
nocomposites (Zhang et al., 2010). Bao et al. reported the preparation
probe for monitoring 2-mercaptobenzothiazole (MBT) and cyanide ions
of high-performance liquid electrolyte-based transistors by depositing
in water samples. The colorimetric sensing principle for MBT and cy-
2D van der Waals materials (MoS2 and graphene) on double-layer
anide is based on the strong affinity of MBT-based thiol groups and
mesoporous nanopaper made of NFC. The graphene liquid crystal tube
cyanide to AgNPs (Golmohammadi, Morales-Narvaez, Naghdi, &
based on nanofibers could be employed for electrical pH sensing (Bao
Merkoci, 2017). The same type composite of AgNPs/BNC was further
et al., 2014).
utilized as a colorimetric platform for the detection of methimazole and
SERS has been considered as one of the most powerful tools for (bio)
iodide, in the range of 0.5–10 μg mL−1 and 0.2–4 μg mL−1, respectively
chemical detection on account of its high sensitivity and selectivity
(Pourreza, Golmohammadi, Naghdi, & Yousefi, 2015). Heli et al found
(Schlucker, 2014). Nanocellulose is an excellent scaffold to fabricate
that AgNPs embedded within BNC could be partially or entirely etched
SERS substrate. Marques et al. reported the first application of AgNPs/
when exposed to corrosive vapour (ammonia). As a result, the popu-
BNC nanocomposites as active SERS substrate for the detection of
lation density of the AgNPs decreased and the interparticle distance

14
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

Fig. 8. (A) Schematic of pH-induced adsorption of CBZ and ATZ on AuNP/BC; (B) Average Raman spectra of CBZ solid, and CBZ on AuNPs/BNC hydrogel; Average
Raman spectra of ATZ solid, and ATZ on AuNPs/BNC hydrogel; (C) Change of signal/background ratio (I1222/I1371 for CBZ and I961/I1371 for ATZ) as a function of
solution pH. (Modified from Wei & Vikesland, 2015 with permission from Nature Publishing Group).

thiosalicylic acid and 2, 2-dithiodipyridine. The detection limits for the significantly increased the tensile strength of WPU-based films at an
above organic analytes reached 10−4 mol dm−3. Amino acids such as L- optimum dosage of 10 wt %. In contrast, the tensile strength of WPU-
phenylalanine, L-glutamine and L-histidine in aqueous solutions could based films decreased with increasing the dosage of AuNPs. The elon-
also be examined at low concentrations (Marques, Nogueira, Pinto, gation at break decreased greatly with increasing NCC content and
Neto, & Trindade, 2008). SERS signal is greatly dependent on the dis- increased slightly with increasing AuNPs content (Liu, Song et al.,
tance between nanoparticles besides the shape and size of nano- 2012). The chemical vapor deposition of a thin TiO2 film on lightweight
particles. In a reported AuNPs-embedded BNC hydrogel, the signal in- NFC aerogels offered a novel type of functional material with photo-
tensity of SERS was significantly enhanced by the spatial deformation/ switching between water-superabsorbent and water-repellent states
contraction of layered 3D structure during drying, which was favored (Kettunen et al., 2011). A flame retardant based on the combination of
by the formation of “hot spots” between nanoparticles. Even analytes NCC and amorphous calcium carbonate (ACC) nanoparticles was also
having low affinity for AuNPs such as phenylacetic acid (PPA) could be reported (Gebauer et al., 2011). Zhan et al. successfully prepared a
detected with this type of SERS substrate (Park, Chang, Jeong, & Hyun, TiO2/NCC nanocomposite membrane with hierarchical architecture,
2013). Particularly high detection sensitivity has been realized based on high roughness, superhydrophilicity and underwater oleophobicity.
nanocellulose-based SERS substrate. Wei et al. mixed analytes with After UV-light irradiation, the resulting membrane exhibited higher
AuNPs/BNC at the suspension pH lower than the pKa of analytes, re- underwater oil contact angles and water fluxes, beneficial for the se-
sulting in a consistently electrostatically aligned carbamazepine (CBZ) lective separation of oil/water emulsions. More importantly, the TiO2/
and atrazine (ATZ) molecules on nanocomposites. The greatly en- NCC membrane could rapidly degrade contaminant (oleic acid) under
hanced SERS intensity and highly reproducible SERS spectra reduced UV-light irradiation, demonstrating the excellent self-cleaning property
the detection limits of CBZ and ATZ as 3 nM and 11 nM, respectively (Zhan et al., 2018). Tables 1–4 summarize the applications of nano-
(see Fig. 8) (Wei & Vikesland, 2015). cellulose loaded with various inorganic nanoparticles.

3.6. Others 4. Outlook

In addition to the various applications described above, nanocellu- Nanocellulose is a new type of nano-biomaterials with high aspect
lose loaded with nanoparticles can also be used for composite re- ratio, large specific surface area, high hydrophilicity, excellent me-
inforcement (Liu, Song et al., 2012; Wu, Saito, Fujisawa, Fukuzumi, & chanical properties, biocompatibility and biodegradability. The nano-
Isogai, 2012), photoswitching (Kettunen et al., 2011), flame retardancy cellulose can be obtained from a number of cellulosic resources and
(Gebauer et al., 2011), and oil/water separation (Zhan et al., 2018). A have various morphological characteristics, such as NCC, NFC and BNC.
composite film was prepared by combining TEMPO-oxidized NCC with The high specific surface area, controllable size and morphology,
flaky montmorillonite (MTM) nanoparticles. When MTM was 5 wt %, template structure, chemical modifiability and other excellent proper-
the composite film had ultra-high tensile strength (509 MPa) and high ties of naocellulose are favored by the loading of nano-structured ma-
Young's modulus (18 GPa), high fracture work (25.6 MJ/m3) and en- terials. After the loading of nano-structured materials on nanocellulose,
hanced oxygen barrier (Wu et al., 2012). Liu et al. used AgNPs/NCC the obtained nanocomposites exhibit numerous innovative properties
nanocomposites as bifunctional nanofillers to improve the mechanical due to synergistic effects, which are unachievable by nano-structured
and antibacterial properties of waterborne polyurethane (WPU). NCC materials alone. The nanocomposites, especially nanocellulose loaded

15
Q. Zhang, et al. Carbohydrate Polymers 229 (2020) 115454

with noble metal nanoparticles, have been widely applied in the fields properties and behavior of wood cellulose nanocrystal suspensions.
of antibacterial, biomedical, protein/enzyme immobilization, catalysis, Biomacromolecules, 6, 1048–1054.
Benaissi, K., Johnson, L., Walsh, D. A., & Thielemans, W. (2010). Synthesis of platinum
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noparticles from a fundamental point of view is also an important re- crystalline cellulose nanobiocatalyst: A highly efficient biocatalyst for dipeptide
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All authors have given approval to the final version of the manuscript. Nanoscale, 8, 13288–13296.
Chen, X., Cheng, L., Li, H., Barhoum, A., Zhang, Y., He, X., et al. (2018). Magnetic na-
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Declaration of Competing Interest Chemistryselect, 3, 9127–9143.
Chetia, M., Ali, A. A., Bordoloi, A., & Sarma, D. (2017). Facile route for the regioselective
The authors declare that they have no competing financial interests. synthesis of 1,4-disubstituted 1,2,3-triazole using copper nanoparticles supported on
nanocellulose as recyclable heterogeneous catalyst. Journal of Chemical Sciences, 129,
1211–1217.
Acknowledgments Chi, K., & Catchmark, J. M. (2017). Crystalline nanocellulose/lauric arginate complexes.
Carbohydrate Polymers, 175, 320–329.
Choi, H. Y., & Jeong, Y. G. (2019). Microstructures and piezoelectric performance of eco-
The support of this work by the Natural Science Foundation of
friendly composite films based on nanocellulose and barium titanate nanoparticle.
Jiangsu Province (BK20171450), National Key Research and Composites Part B: Engineering, 168, 58–65.
Development Program of China (2017YFD0601005), and Natural Cirtiu, C. M., Dunlop-Briere, A. F., & Moores, A. (2011). Cellulose nanocrystallites as an
Science Foundation of China (No. 61571239) are gratefully acknowl- efficient support for nanoparticles of palladium: Application for catalytic hydro-
genation and heck coupling under mild conditions. Green Chemistry, 13, 288–291.
edged. Czaja, W. K., Young, D. J., Kawecki, M., & Brown, R. M., Jr. (2007). The future prospects
of microbial cellulose in biomedical applications. Biomacromolecules, 8, 1–12.
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