Foodchem D 24 01403 Reviewer

Food Chemistry
Functional black phosphorus-based sensors for food safety applications: a review

--Manuscript Draft--
Manuscript Number: FOODCHEM-D-24-01403
Article Type: Review Article
Keywords: Black phosphorus; Preparation; Function; Sensors; Food safety
Abstract: Food safety has garnered global attention, necessitating advanced methods for the
quick and accurate detection of contaminants. Sensors, notable for their ease of use,
high sensitivity, and fast analysis, are prominent. 2D nanomaterials like graphene have
been employed to improve sensor performance. Particularly, black phosphorus (BP)
stands out with its multifunctional capabilities, attributed to unique layered structure,
ultra-high charge mobility, easy surface functionalization, enhanced optical absorption,
and tunable direct bandgap. These characteristics suggest that BP could significantly
enhance sensor selectivity, sensitivity, and response speed for contaminant
detection. Despite numerous studies on BP-based sensors in food safety, few reviews
have been comprehensively summarized. Moreover, challenges in BP’s preparation
and stability restrict its wider use. This paper reviews recent research on BP’s role in
food safety, covering preparation, passivation, and applications. Through analysis of
challenges and prospect, this review aims to provide insightful guidance for upcoming
research in this area.
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Highlights (for review)
Highlights
 A introduction to the latest advances in BP preparation methods was provided.
 The recent advances in the surface engineering for passivation was discussed.
 The latest progress on BP-based materials in food safety applications was
summarized.
 BP remarkable versatility in applications was exhibited.
 The respective practicality, limitations, and challenges were discussed.

Manuscript Click here to view linked References
1 Functional black phosphorus-based sensors
2 for food safety applications: a review
4 Wei Han a, Peiyuan Wei a, Lingling Xie c, Limin Zhu a,*,
5 Baoshan He b,*, Xiaoyu Cao a,*
a
9 School of Chemistry and Chemical Engineering, Henan University of Technology,
10 Zhengzhou, Henan 450001, PR China

b
11 School of Food Science and Technology, Henan University of Technology,
12 Zhengzhou, Henan 450001, PR China

c
13 School of Environmental Engineering, Henan University of Technology, Zhengzhou,
14 Henan 450001, PR China
15
16
17
18
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20 * Corresponding author. E-mail address: [email protected] (X. Cao),
21 [email protected] (B. He), [email protected] (L. Zhu).
22
23
1
24 Abstract
25 Food safety has garnered global attention, necessitating advanced methods for the
26 quick and accurate detection of contaminants. Sensors, notable for their ease of use,
27 high sensitivity, and fast analysis, are prominent. 2D nanomaterials like graphene have
28 been employed to improve sensor performance. Particularly, black phosphorus (BP)
29 stands out with its multifunctional capabilities, attributed to unique layered structure,
30 ultra-high charge mobility, easy surface functionalization, enhanced optical absorption,
31 and tunable direct bandgap. These characteristics suggest that BP could significantly
32 enhance sensor selectivity, sensitivity, and response speed for contaminant detection.
33 Despite numerous studies on BP-based sensors in food safety, few reviews have been
34 comprehensively summarized. Moreover, challenges in BP’s preparation and stability
35 restrict its wider use. This paper reviews recent research on BP’s role in food safety,
36 covering preparation, passivation, and applications. Through analysis of challenges and
37 prospect, this review aims to provide insightful guidance for upcoming research in this
38 area.
39 Keywords
40 Black phosphorus; Preparation; Function; Sensors; Food safety
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48 1. Introduction
49 Common chemical substances like toxins, veterinary drugs, pesticides, and heavy
50 metals inevitably pollute most foods, during planting, packaging, and production
51 processes. The presence of these contaminants in the human food chain highlights the
52 critical significance of food safety, an issue that has attracted considerable public
53 interest (Lin, Yan, Zhao, Duan, Wang, & Wu, 2023). Consequently, reliable and
54 convenient detection techniques for the quantitative assessments of food contaminants
55 are crucial. While traditional methods such as mass spectrometry and chromatography
56 (Interino et al., 2023; García, León, Armenta, & Pardo, 2023) are prevalent, they face
57 challenges like laborious sample preparation, complex instrument operations, and
58 limited on-site screening capabilities. Sensor-based analytical methods, offering
59 advantages in terms of cost, sensitivity, and accuracy, present a promising solution to
60 these challenges.
61 Numerous nanomaterials have been extensively employed to improve the
62 analytical performances in sensing platforms (Li et al., 2020; Zhang et al., 2022).
63 Notably, black phosphorus (BP) is emerging as a single-element two-dimensional (2D)
64 layered nanomaterial and has been studied extensively since 2014. Owing to its unique
65 structure and outstanding physicochemical properties, BP can perform various
66 functions in food safety analyses. As shown in Fig. 1A, each P atom forms sp3 covalent
67 bonds in every layer with three adjacent P atoms, affording a puckered honeycomb
68 structure distinct from conventional 2D materials. This structure can be employed to
69 modify electrodes and immobilize signal molecules or target recognition units, and has
70 the characteristics of high specific surface area, multiple adsorption sites, and good
71 adsorption performance (Du, Lin, Xu, & Chu, 2015). Meanwhile, in addition to having
72 an approximately 20 times higher molar response coefficient than graphene (Gr) and
3
73 MoS2, which represents the intrinsic sensing ability of the same number of molecules
74 (Shuai et al., 2023), BP also possesses high current switching ratios and layer-
75 dependent band gaps, facilitating the detection of targets by tracking the changes in
76 conductance, resistance, and other photoelectric response parameters (Fig. 1B)
77 (Castellanos-Gomez, 2015). Compared to other 2D materials, BP exhibits a higher
78 extinction coefficient and photothermal conversion efficiency. It can be used to
79 fabricate photothermal sensing probes and be combined with other signal detection
80 systems to create multimodal sensors, which can enhance accuracy and reliability via
81 inter-calibration (Wang, Li, & Zhang, 2023). Additionally, BP provides more sensitive
82 responses to the strain magnitude and direction than other 2D materials, owing to the
83 strong anisotropy resulting from the zigzag and armchair structures (Fig. 1C). This
84 allows for the tensile or compression deformation of BP along any arbitrary direction,
85 providing excellent mechanical flexibility (Vaquero-Garzon, Frisenda, & Castellanos-
86 Gomez, 2019). Consequently, functional BP presents a viable option for constructing
87 sensors with excellent selectivity, high sensitivity, and fast response times to achieve
88 contaminant identification in intricate food samples. Numerous studies have applied BP
89 and its derivatives for food safety detection. However, few reviews have systematically
90 summarized the recent research progress in functional BP-based sensors for quantifying
91 food chemical contaminants. Furthermore, promoting practical applications of BP is
92 impeded by two main inherent restrictions. One is the lack of prolonged stability of BP
93 under environmental circumstances, and the other is that effective strategies for
94 synthesizing BP with good crystallinity, reproducibility, and wafer scale are
95 unavailable. To date, considerable research has been devoted to producing high-quality
96 BP in a cost-effective manner and developing surface/interface-engineering-based
97 passivation methods. Thus, despite the explosive growth of BP research and its great
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98 potential in food safety applications, studies on the basic characteristics and
99 applications of this intriguing nanomaterial are still in their infancy.
100
101 Fig. 1. A. Structure of BP (Du et al., 2015). B. Current on/off ratio versus carrier mobility of
102 comparison among graphene, transition metal dichalcogenides, and BP-based field effect transistors
103 (Castellanos-Gomez, 2015). C. Schematic of the process of a flexible electronic device fabricated
104 based on the mechanical properties of BP (Vaquero-Garzon, 2019).
105 To address these issues, this review presents a state-of-the-art description of BP
106 preparation methods and passivation techniques, as well as an analysis of the utility and
107 limitations of these methods (Scheme 1). Based on the properties and functions of BP,
108 recent advances in functional BP-based sensors for food safety applications are
109 systematically reviewed. Finally, the expected directions for the development of BP
110 and its derivatives are discussed to further enhance the performance of BP-based
111 sensors. We aim to offer fundamental insights into the efficient application of this
112 critical and distinct nanomaterial in food safety assessments.
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113
114 Scheme 1. BP preparation, passivation, and food safety applications.
115 2. Preparation
116 Owing to its puckered layer structure and the van der Waals (vdW) bonds between
117 the stacked layers, bulk BP is easily exfoliated into single- or few-layered nanosheets.
118 Generally, the synthesis protocols for BP can be classified into top-down exfoliation
119 and bottom-up assembly (Table 1). Top-down exfoliation uses an external force to
120 cleave the vdW bonds in bulk BP. The synthesis is applied to materials with layered
121 crystal structures (Zhang and Sun, 2021). While bottom-up assembly involves
122 atomization and reassembly of P sources, it is suitable for layered and non-layered
123 structures.
124 2.1 Top-Down exfoliation
125 Conventional mechanical microcleavage is a scotch-tape-based exfoliation
126 method that peels off the BP layers from a bulk crystal and transfers them onto a
127 substrate (Liu et al., 2014). Recently, numerous mechanical-exfoliation-based thinning
128 processes have successfully produced thin-layered BP. For example, Ar+ plasma
129 etching (Fig. 2A) (Lu et al., 2022), laser pruning (Lu et al., 2015), and wet chemical
6
130 thinning (Fan et al., 2019) can be used to effectively design a preset number of layers.
131 In liquid exfoliation, organic solvent cavitation generates a bubble burst shock-
132 wave-stripped BP with a solvated shell to protect BP from oxygen and water (Fig. 2B).
133 Because the surface free energy of BP (90 mJ/m2) is much higher than that of commonly
134 used organic solvents (20–50 mJ/m2) (Kang et al., 2015), many studies have focused
135 on the use of organic solvents with high surface tension to reduce preparation costs and
136 prevent reaggregation (Guo et al., 2015). Recent studies have shown that the exfoliation
137 efficiency and stability can be improved using additives, such as surfactants, ionic
138 liquids, and polymers. Xu et al. added phytic acid, a hydroxyl- and phosphorus-rich
139 polar small molecule to DMF to increase the solubility of BP, affording BP with 6–8
140 layers and a transverse size of tens of micrometers (Xu et al., 2016). Xiao et al. used
141 non-volatile recyclable ionic liquids to prepare BP with a thickness of 1.3 to1.75 nm
142 and lateral dimensions of 300 to 900 nm. In particular, in 1-buthyl-3-
143 methylimidazolium hexafluorophosphate ([BMIM]PF6), the yield increased to 28%
144 (Xiao et al., 2023). Zhang et al. added polyvinylpyrrolidone (PVP) to ethanol, achieving
145 a monolayer yield of up to 51%. After 20 d, approximately 90% remained stable (Zhang
146 et al., 2017).
147 Electrochemical delamination utilizes electrolytes to stimulate ions in the solution
148 for intercalation into the precursors and subsequently to form nanostructures. By
149 regulating the parameters (e.g., voltage or current) and electrolyte species, products
150 with different conductivities, oxygen contents, defect densities, and thicknesses can be
151 obtained and the morphology of BP can be controlled, including BP quantum dots,
152 holey BP, and 3D BP. Based on the position of the raw stripping materials,
153 electrochemical exfoliation can be categorized as the anode (Ambrosi, Sofer, & Pumera,
154 2017), cathode, or electrolyte (Fig. 2C) exfoliation methods (Yang et al., 2019). In
7
155 contrast to anodic and electrolytic exfoliation, cathodic exfoliation does not involve
156 oxygen-based radical generation. Therefore, the products exhibit low oxidation rates
157 and no surface defects (He et al., 2020). Wang et al. successfully prepared large-area
158 crystalline BP with an average domain size of 77.6±15.0 µm by weak Lewis acid tetra-
159 n-butylammonium acetate, which provided a new approach to producing BP with a
160 large size and high crystallinity (Wang et al., 2021a). However, this approach is still
161 nascent compared to Gr (Mohanty et al., 2012), owing to the multi-step process and the
162 difficulty in controlling the edges.
163 2.2 Bottom-up assembly
164 In chemical vapor deposition (CVD), a precursor is evaporated and re-condensed
165 to form nanostructures on substrate surfaces in specific atmospheres at controlled
166 temperatures and pressures (Cai, Liu, Zou, & Cheng, 2018). Impressed by the wafer-
167 scale growth of carbon nanomaterials with exceptional properties using CVD (Li et al.,
168 2022b), it is supposed to use the same method to create large-scale BP. However, the
169 synthesized products achieved by Smith et al. using SnI4/Sn as a mineralizer (Smith,
170 Hagaman, & Ji, 2016) and Xu et al. using the epitaxial nucleation method (Xu, Zheng,
171 Liang, & Li, 2020) did not satisfy the expected horizontal scale. The high pressure
172 required to form the BP phase may result from its unique sp3 hybrid structure, which is
173 challenging to achieve experimentally, leading to a higher surface energy than that of
174 the substrates and limiting transverse growth (Shriber, Samanta, Nessim, & Grinberg,
175 2018). To overcome these difficulties, Wu et al. proposed a pulsed laser deposition
176 strategy that utilized an ultrahigh-uniformity mica wafer as substrate and a laser to
177 bombard objects into plasma, instead of using conventional heating mode, and obtain
178 BP with increased transverse dimensions from tens of micrometers to centimeters (Fig.
179 2D) (Wu et al., 2021b). This is of great significance for further exploring large-scale
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180 BP, but considerable research efforts are needed compared with Gr (Liu, Cheng, Zhao,
181 Wang, & Li, 2022).
182
183 Fig. 2. Schematic of BP preparation. A. Ar+ plasma etching (Lu et al., 2022). B. Liquid exfoliation
184 (Xiao et al., 2015), including (a) schematic of the weak interaction between the ionic liquid and BP,
185 (b) comparison of different ionic liquids before and after stripping, (c) insertion free energy of
186 different ionic liquids, (d) proportion of the length distribution, and (e) height profile showing the
187 characterization of BP systems that have been exfoliated in ionic liquid. C. Cathode exfoliation
188 process, and XPS spectra of BP (Yang et al., 2018). D. Pulsed laser deposition. Photos displaying
189 the different obtained thicknesses of BP (Wu et al., 2021). E. Solvothermal method (Zhu et al.,
190 2020).
191 The wet chemical method, including solvothermal, hydrothermal, and template
192 synthesis, has become a common approach for fabricating nanosheets and
193 heterojunctions (Liu, Shi, Wang, Weng, & Che, 2019; Chouat, Nguyen, Mohan, & Do,
194 2022). Generally, it involves an evaporation–condensation-driven solid–vapor–solid
195 process. For instance, NH4F was added to reactants to lower the surface activation
196 energy of red phosphorus (RP) and thus the temperature to 200 ℃ in an autoclave (Zhao,
197 Wang, Shao, Wu, Huang, & Hao, 2017). Nucleophilic reagents have been used to
9
198 reduce the precursor surface activation energy and the reaction temperature. Zhu et al.
199 reacted ethylenediamine with RP to form polyphosphate ions, from which BP was
200 produced at a significantly reduced temperature (140 – 170 °C) (Fig. 2E) (Zhu, Liang,
201 Xu, Fu, & Xiao, 2020).
202 Table 1. Comparison of the different preparation methods of BP.
Techniques Method Thickness Characteristics Ref.

Top-down exfoliation
scotch-tape 4–6 nm (Liu et al., 2014)
good crystal
Mechanical Ar+ plasma etching 0.5–2.7 nm (Lu et al., 2022)
structure; easily
microcleavage laser pruning – (Lu et al., 2015)
oxidized; low yield.
wet chemical ~4 nm (Fan et al., 2019)
thinning (Woomer et al.,
organic solvents:
scalable; simple; 2015; Brent et al.,
NMP, CHP, ~20 nm
benzonitrile, etc. time- consuming; 2014; Yasaei et al.,
Liquid
poor crystal 2015)
exfoliation
additives: surfactants, quality; difficult (Xu et al., 2016;
ionic liquids, and ~10 layers purify. Xiao et al., 2023;
polymers Zhang et al.,
Electro- anodic exfoliation high yield; rapid; 2017)
(Yang et al., 2018;
chemical cathodic exfoliation ~15 layers high quality; Wang et al.,
delamination electrolyte uneven size. 2021a)
Bottom-up assembly
exfoliation
mineralizer-assisted 0.6–200 large area; poor (Smith et al.,
CVD phase
pulsedtransition
laser nm crystal quality. 2016)
(Wu et al., 2021b)
deposition high yield;
sublimation-induced
Wet chemical ~5 nm uniform size; poor (Zhu et al., 2020)
phase transition
crystal quality.
203 3. Surface/Interface Engineering for Passivation
204 Another issue associated with BP is that it degrades quickly owing to the presence
205 of electron lone pairs, which redistribute and engage in covalent interactions under
206 ambient conditions (Ryder, Wood, Wells, & Hersam, 2016). Numerous studies have
207 been conducted to determine the exact degradation mechanism of this system. Zhou et
208 al. proposed that the degradation involved light-induced oxidation under light, oxygen,
209 and water exposure, which was a generally accepted theory (Fig. 3A) (Zhou, Chen,
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210 Tong, & Wang, 2016). However, recent studies have revealed that upon exposure to
211 water without light or oxygen, BP can also decompose and form different substances
212 (Fig. 3B) (Zhang et al., 2018). Various strategies have been proposed for effective
213 passivation via surface/interface engineering, including organic functionalization,
214 inorganic coating, nanomaterials integration, and biological strategies.
215 3.1 Organic functionalization
216 Functionalization with organic molecules has proven an effective and controllable
217 approach to improve stability, given the large number of free lone pair electrons on BP.
218 Thurakkal and Zhang introduced aromatic diazo substituents to the BP surface via a
219 free-radical mechanism, forming P–C bonds. This prevented chemical degradation
220 from oxygen and water while maintaining BP stability for 15 d (Thurakkal and Zhang,
221 2021). Sofer et al. introduced a hydroxyl group on the BP surface by forming P–O–C
222 bonds between the alkyl halide and BP surface via a nucleophilic substitution reaction
223 (Sofer et al., 2017). Based on ab initio studies, nucleophilic substitution had a greater
224 impact than free radical reactions. However, both methods resulted in the P atoms
225 retaining an unsaturated coordination state, which may influence the passivation effect.
226 Liu et al. reacted BP with 4-azidobenzoic acid to form P=N bonds, promoting the
227 saturation of the P atom coordination state, such that BP could be stored stably for more
228 than 21 d under environmental conditions (Liu et al., 2019). Surprisingly, covalent
229 functionalization is challenging despite the high reactivity afforded by lone pair
230 electrons. The number of reactions available for covalent functionalization is limited.
231 Covalent functionalization produces more stable products than noncovalent
232 functionalization, but significantly impacts the original conjugated structure of BP,
233 which in turn affects its electrical conductivity (Ryder et al., 2016). Noncovalent
234 functionalization can preserve its intrinsic properties because only physical barriers
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235 with relatively weak interactions are introduced on the surface of BP. Apart from lone
236 pair electrons, lattice defects such as P vacancies are introduced during BP preparation,
237 which also have high reactivity and mobility. They tend to adsorb organic molecules
238 resulting in various diverse interactions. For example, positively charged polymers
239 such as polydopamine (PDA) (Xu et al., 2020), poly (3,4-ethylene dioxythiophene)
240 (PEDOT), poly (styrene sulfonate) (PSS) (Li, Chou, Wang, Liu, & Dou, 2013), poly-
241 L-lysine (PLL) (Zhao et al., 2018), polypeptide (PP) (Kumar, 2019), polypyrrole (PPy)
242 (Zhang, Li, Xu, & Wen, 2017), and poly(diallyl dimethylammonium chloride) (PDDA)
243 (Zhen, Tang, Tao, & Zhao, 2019) have been used for synthesizing hybrids via
244 electrostatic interactions with negatively charged BP, coating BP in the liquid
245 exfoliation process to enhance stability. Although the protection was only effective on
246 the basal plane, the edges were still vulnerable to deterioration (Kang et al., 2015).
247 Another effective method to modify organic molecules in a noncovalent manner is
248 through the vdW interactions. Bolognesi et al. delayed BP oxidation in the air for 18 h
249 using a multilayer film composed of electrically insulating linear alkanes (Bolognesi et
250 al., 2019a). Liang et al. proposed coating BP with hexamethylenediamine (HA) to
251 maintain its sharpness in aqueous solution for over a month (Fig. 3C) (Liang, Wu, Liu,
252 Li, Chen, & Zhang, 2019). Yuan et al. utilized a self-assembly method of anthraquinone
253 compounds to safeguard the surface of BP from degradation (Yuan, Tang, Yang, Hua,
254 Yin, & Xia, 2020). Moreover, noncovalent functionalization with functional organics
255 can produce multifunctional systems. Electrochemical redox mediators like thionine
256 (Song, Ma, & Ye, 2020), fluorescent molecules such as pyrene derivatives (Bolognesi
257 et al., 2019b), and 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) (Wang et
258 al., 2017) are reported to have produced highly stable systems with efficient sensing
259 capabilities.
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260 3.2 Inorganic modification
261 Here, inorganics primarily include metal oxides and metals, and the term ‘metal’
262 refers to the doping and coordination interactions.
263 Metal oxides, such as AlOx (Xiong et al., 2020), Cs2CO3 (Xiang et al., 2015), and
264 HfO2 (Haratipour, Robbins, & Koester, 2015), can be used as physical barrier
265 membranes on BP. They modulate the carrier type, density, and mobility of the
266 underlying layers without affecting the crystal lattices. Significant enhancement in
267 stability comes at a cost of reduced sensitivity owing to the hampered interaction
268 between BP and targets (Miao, Cai, Zhang, Nah, Yeom, & Wang, 2017).
269 The interaction between metal and BP is a common passivation technique owing
270 to their unique structure and characteristics, which results in a deeper and more
271 pluralistic interaction compared to that of flattened Gr and metal (Chen, Jin, Yang, &
272 He, 2022). Such modification can improve the stability and several other properties,
273 including magnetism, absorptive selectivity, thermal and electrical conductivities, and
274 light absorption capacity. Intercalation doping and surface charge transfer doping are
275 the main doping reaction types. Intercalation doping involves the insertion of metal
276 atoms into the BP interlayer space. Alkali metal elements, such as Li, Na, K, Rb, and
277 Cs, are easy to incorporate owing to their small atomic radius (Tan et al., 2018). The
278 insertion rate has an impact on the structure and electronic state of BP. Under the
279 conditions of a low doping density, the original structure of BP was approximately
280 maintained and the electrical conductivity of BP was improved. In contrast, under a
281 high density, P–P bonds would be broken by alkali metals. Surface charge-transfer
282 doping involves the electron transfer between the two materials, which occurs more
283 frequently. Group IB metal ions (Cu2+, Ag+, and Au3+) adsorb on the BP surface via
284 cation–π interactions and passivate the lone pair electrons on P atoms (Lin et al., 2019).
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285 Additionally, based on the Lewis acid-base hypothesis, the vacant orbitals of Lewis
286 acidic metal ions can accept the lone pair electrons from Lewis basic P atoms (Fig. 3D)
287 (Tofan et al., 2021). Chelating agents can simply remove the bonded metals.
288 3.3 Nanomaterials integration
289 The vdW heterojunctions with nanomaterials and BP have attracted considerable
290 attention owing to their simple formation and favorable synergistic effects. Since any
291 passivated dangling-bond-free surface can respond to another surface via vdW forces,
292 BP can theoretically be easily integrated with other nanomaterials to form the vdW
293 heterojunctions without adhering to strict lattice matching and processing compatibility
294 (Ke, Nguyen, Fan, Li, Wu, & Hu, 2020). Transition metal dichalcogenides (TMDs) can
295 be integrated to form the vdW heterojunctions (Li, Wang, Chen, Zhou, & Zhang, 2017).
296 An insulating material, hexagonal boron nitride (h-BN), is employed to encapsulate BP
297 to create a sandwich structure that behaves as a dielectric layer and exhibits stable
298 responses (Constantinescu and Hine, 2016; Cao et al., 2015).
299 In addition to vdW heterojunctions, non-vdW heterojunctions also hold significant
300 potential. The UiO–66 metal organic framework (MOF) has been used to synthesize
301 UiO–66@BP nanohybrids via emulsification. A P–O–Zr covalent bonding bridge was
302 formed at the oil/water interface to stabilize BP in the air (Huang, Wang, & Fu, 2023).
303 Additionally, heterojunctions formed between BP and different types of carbon
304 nanomaterials have garnered considerable attention (Fig. 3E) (Cai et al., 2019a; Cai,
305 Xia, & Jin, 2019; Li, Chou, Wang, Liu, & Dou, 2013; Wen et al., 2019). Notably, BP
306 can form a heterojunction with Gr through P-C and P-O-C covalent bonds (Shen, Liu,
307 Wu, & Yang, 2022). Owing to the high carrier mobility and stability of Gr, this method
308 improves the stability of BP, and enhances electrochemical performance through
309 synergistic effects.
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310 3.4 Biological strategies
311 The highly reactive BP surface can also adsorb biomolecules at the cavity sites,
312 thus improving its stability and biocompatibility (Qu et al., 2020). Singh et al.
313 discovered that degradation spots generated by photooxidation could be removed by β-
314 carotene treatment (Singh et al., 2023). This aspect undoubtedly provides more ideas
315 for the development of passivation methods (Fig. 3F).
316
317 Fig. 3. Schematic of BP’s surface/interface engineering. A. Light-induced oxidation degradation
318 (Zhou et al., 2016). B. pH-Dependent degradation (Zhang et al., 2018). C. HA-coated BP for
319 passivation (Liang et al., 2019). D. Group 13 Lewis Acids for the passivation of BP, ordered by their
320 relative effectiveness based on TEM and AFM (Tofan et al., 2021). E. Integration of porous graphene
321 and BP (Cai et al., 2019). F. Repairing and preventing photooxidation with β-carotene (Singh et al.,
322 2023).
323 4. Applications in Food Safety
324 Most agricultural products are inevitably exposed to food contaminants such as
325 toxins, veterinary drugs, pesticides, and heavy metals, which pose significant threats to
326 the environment and human health. Utilizing the functionality of BP, researchers have
327 developed numerous BP-based sensors for the detection of food contaminants.
328 Representative examples are discussed in this section, and Table 2 provides an outline
329 of the various applications of these systems.
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330 4.1 Detection of toxins
331 The toxins referred to here are agricultural and marine toxins in nature.
332 Agricultural toxins, primarily mycotoxins such as ochratoxin A (OTA), patulin (PAT),
333 aflatoxin (AF), and zearalenone (ZEN), are produced in the majority of agricultural
334 products and can negatively affect humans via the food chain. Marine toxins such as
335 okadaic acid (OA) can accumulate in the tissues of marine species, and consumption of
336 seafood contaminated with marine toxins can lead to various poisoning symptoms.
337 OTA. BP is inherently unstable in environmental conditions, limiting its direct use
338 in the large-scale production of chemically modified electrodes. To enhance its stability,
339 one common approach involves combining BP with noble metals. This combination
340 passivates the lone pair electrons of BP through cation-π interactions with noble metal
341 ions, significantly increasing BP’s stability. Furthermore, merging the high electrical
342 conductivity of noble metals with BP’s large specific surface area creates a synergistic
343 effect, enhancing electrical activity. For instance, Xiang et al. developed an Ag+-
344 functionalized BP-based voltametric sensor for the detection of OTA, demonstrating
345 notable cycling stability and anti-fouling ability in oxygen-rich aqueous solutions
346 (Xiang, Belen-Camarada, & Wen, 2018). The strong cationic interactions and the large
347 surface areas of these composites reduced OTA oxidation product adsorption on the
348 electrode surface, thereby minizing electrode contamination. However, the sensor still
349 suffered from high interference due to its elevated oxidation potential. Another noble
350 metal is Au, has been effectively used with BP. Jiang et al. constructed a BP-AuNP-
351 based double-layer structured paper nanobiosensor for the simultaneous detection of
352 OTA and AFB1 (Jiang, Guo, Liu, Qin, Bikila, & Weng, 2022). The BP-AuNP
353 composition firmly anchored the aptamer (Apt) via Au-S bonds and promoted electron
354 transfer, improving the current response of signal probes. The BP-AuNP-Apt system,
16
355 screen printed on a paper substrate for easy operation, can detect both toxins within 15
356 minutes. Additionally, combining carbon materials with BP is also prevalent. Li et al.
357 created a lable-free aptasensor leveraging the high conductivity of carbon dots and the
358 large surface area of BP. They synthesized BP-carbon dot 0D/2D nanohybrids via
359 simple in situ polymerization. The composites’ ultra-high specific surface area
360 provided numerous binding sites for Apt, allowing the sensor to detect OTA with a
361 remarkably low limit of detection (LOD) of 0.03 fg/mL (Li, Qiao, Zhao, He, Sheng, &
362 Yue, 2021).
363 ZEN. BP-AuNP not only facilitates electron transfer but also serves as an effective
364 fluorescence burst probe. Li et al. designed a novel fluorescence
365 immunochromatographic sensor (FICS) utilizing the fluorescence bursting effect of
366 BP-AuNP on ZnCdSe/ZnS quantum dots to detect ZEN. The process involved reducing
367 AuNP on the BP surface to create BP-AuNP nanocomposites, followed by synthesizing
368 BP-AuNP-Ab, capitalizing on BP-AuNP’s ample antibody adsorption sites. Energy
369 transfer interactions between the quantum dots (energy donors) and BP-AuNP (energy
370 acceptors) reduced the fluorescence signal. The presence of ZEN, binding to BP-AuNP-
371 Ab, altered the fluorescence intensity. Notably, BP-AuNP demonstrate superior
372 fluorescence quenching efficiencies, 1.73 and 1.44 times higher than AuNPs and BPs
373 respectively (Li, Zhang, Wang, Wen, & Wang, 2020). Besides, graphene oxide (GO),
374 another carbon material, can also be combined with BP. Hu et al. synthesized BP-GO
375 composites using a hydrothermal method to construct ratiometric electrochemical
376 sensors (Fig. 4A) (Hu, Tang, Xia, Liu, Zhao, & Zeng, 2022). BP and GO, with similar
377 layered structures, offer high surface area and excellent conductivity. Their
378 combination yields composites with enhanced electron transfer and electrocatalytic
379 performance. In this system, ZEN acted as the response signal, while methylene blue
17
380 (MB) acted as the internal reference. As ZEN concentration increases, its peak current
381 increased, and the MB signal decreased due to increased resistance. This ratiometric
382 electrochemical sensor could improve the accuracy. Notably, the combination of the
383 two also improved the stability of the sensor. Even after 20 d, the sensor retained 94.7%
384 of its initial responsivity.
385 4.2 Detection of veterinary drug residues
386 Veterinary medications are crucial in the prevention and treatment of animal
387 diseasess, as well as improving animal productivity and the quality of animal products.
388 However, the abuse or misuse of these medications results in the presence of drug
389 residues in animal-derived food products and the surrounding environment, posing a
390 risk to humans. Among veterinary drugs, the following are at increased risk of residue
391 exceedances in products of animal origin: antibiotics such as tetracycline (TC);
392 fluoroquinolones such as norfloxacin (NOR), enrofloxacin (ENR), and pefloxacin
393 (PEF); hormone medications such as clenbuterol (CLB), ractopamine (RAC),
394 diethylstilbestrol (DES), and 17 β-estradiol (E2); and fungicides such as malachite
395 green (MG).
396 4.2.1 Antibiotics
397 TC. Chen et al. devised a water-stable BP field-effect transistor (FET) sensor using
398 an innovative surface engineering strategy and sensing mechanism (Fig. 4B) (Chen et
399 al., 2023). Their approach involved initially coordinating Ag+ with BP, followed by
400 adsorbing a supramolecular mixture (MC) of cyanuric acid and melamine onto the Ag+-
401 BP compound. This MC network augmented the stability of BP and exhibited superior
402 thickness and homogeneity over the previously reported Al2O3 layer, thus maintaining
403 the electrical characteristics of BP. Additionally, the interaction of molecularly
404 imprinted polymers (MIPs), serving as probes, with TC, modified the electronic energy
18
405 of these probes. This change in electronic properties facilitated the effective detection
406 of TC.
407 4.2.2 Fluoroquinolones
408 NOR. Ren et al. developed a lateral flow immunoassay strip (LFIS) with
409 innovative colorimetric/photothermal dual readout models for detecting NOR (Fig. 4C)
410 (Ren et al., 2021). This was the first application of BP, known for its outstanding optical
411 and thermal properties, as a dual-mode detection agent in LFIS. In the colorimetric
412 model, the involvement of BP significantly amplified the visible color change, elevating
413 the sensitivity of detection. In the photothermal aspect, BP efficiently converted
414 absorbed light energy into heat in less than 1 min. This efficiency enabled the
415 completion of the detection process within 20 min. The dual readout models
416 considerably improved the sensitivity and accuracy of the BP-based sensor. The results
417 indicated that the LOD of this strip was about a hundred times better than that of
418 conventional strips.
419 ENR. Li et al. crafted a non-enzymatic photothermal immunosensor using BP-
420 PtNP nanocomposites for detecting ENR in animal-derived food products (Li, Wen,
421 Guo, Wang, & Wang, 2021). They utilized BP's inherent instability to synthesize finely
422 dispersed PtNP directly on its surface (Fig. 4D). BP's large surface area, combined with
423 its excellent electrical and thermal conductivity, synergized with PtNP's exceptional
424 catalytic properties. This combination greatly enhanced the catalytic activity,
425 mimicking natural enzymes. This novel approach effectively supplanted the need for
426 delicate and costly biological enzymes, intricate enzyme labeling techniques, and
427 elaborate purification processes. Additionally, the enhanced activity of this nanozyme
428 markedly improved the specificity and sensitivity of the detection method, especially
429 in complex biological matrices like animal-derived foods.
19
430 4.2.3 Hormones
431 CLB. Ge et al. created an electrochemical sensor for CLB detection by integrating
432 BP with the nonconductive polymer Nafion (Nf) (Ge et al., 2018). This modification
433 with Nf enhanced the electrode's stability, yielding a peak current's relative standard
434 deviation of less than 5% over a 5-d stability test. However, the poor conductivity of
435 Nf negatively impacted the sensitivity of the sensor.
436 RAC. Ge et al. prepared composite-film-based electrochemical sensors decorated
437 with mono(6-mercapto-6-deoxy)-β-cyclodextrin (S-β-CD), PEDOTNPs, and BP for
438 simultaneous detection of RAC and CLB (Ge et al., 2019) (Fig. 4E). The films showed
439 improved reaction rates for RAC and CLB, and decreased overpotentials for their
440 oxidation, thanks to the synergistic effects of the extraordinary electrical
441 conductivity of PEDOTNPs, the excellent electrocatalytic activity and good host
442 recognition of S-β-CD, and the strong electron transfer ability and large specific surface
443 area of BP. Remarkably, surface fouling from electrochemical reaction byproducts was
444 effectively cleared by repeated cyclic voltammetric scans. However, the complexity of
445 fabricating these electrodes may limit their practical application.
446 4.3 Detection of pesticide residues
447 The use of pesticides is required for better crop growth. However, the overuse can
448 leave residues in food that can have a serious impact on the soil environment and the
449 quality of agricultural products. Therefore, an accurate analytical method is required to
450 detect trace pesticides. BP-based sensors have been used for pesticide detection,
451 including growth regulators such as α-naphthaleneacetic acid (NAA); herbicides such
452 as maleic hydrazide (MH) and paraquat (PQ); and pesticides such as carbendazim (CD),
453 acetamiprid (ACE), malathion (ML), and methyl parathion (MP).
20
454 NAA. The trend in detection technology is toward miniaturization and portability
455 (Koo, Wee, Wang, & Trau, 2017). Zhu et al. developed a portable wireless smart
456 nanozyme sensing system for ultratrace detection of NAA (Zhu et al., 2021). They
457 introduced a novel method where CuCl was added to the NMP solution during
458 ultrasonic liquid-phase exfoliation of BP. This step triggered a disproportionation
459 reaction, producing Cu(II) ions that interacted with BP to inhibit the degradation and
460 induce positive charges. This led to the formation of stable BP/Ti3C2-MXene
461 nanohybrids by creating P-Ti and Ti-O-P bonds between the negatively charged Ti3C2-
462 MXene and the positively charged BP (Fig. 4F). The modified electrodes demonstrated
463 robust environmental stability, maintaining intact in humid air at 4 ℃ for up to 8 d. The
464 Ti3C2-MXene/BP nanohybrids displayed oxidase-like characteristics, pivotal for the
465 electrocatalytic oxidation of NAA. Integrated onto flexible electrodes composed of
466 laser-induced porous graphene (LIPG), the system also featured cutting-edge
467 technologies like machine learning algorithms, wireless signal transmission, and
468 portable electrochemical devices, enabling rapid, efficient, and intelligent detection of
469 NAA.
470 4.4 Detection of heavy metal ions
471 Hg2+. The accumulation of heavy metals in the food chain is a critical health
472 concern, necessitating effective preventive measures. BP has shown great promise in
473 ion sensors. Li et al. pioneered a suspended BP FET sensor operating in the
474 subthreshold region and conducted an in-depth study of its mechanism (Li, Zhang,
475 Jiang, Zong, & Cao, 2017). They discovered that upon adsorption of Hg2+ onto BP, the
476 surface charge gating effect altered the conductivity of the sensor carrier density,
477 thereby altering its conductivity. This effect was more pronounced in suspended BP
478 sensors due to the lack of substrate scattering and BP's large surface area, significantly
21
479 enhancing sensitivity. Remarkably, the sensor detected trace Hg2+ in just 3 seconds with
480 a LOD of 0.01 ppb, far below the World Health Organization's safety threshold of 1
481 ppb. Besides, BP's sensitivity and stability under mechanical strain enable the
482 development of flexible sensors. Li et al. fabricated a flexible integrated sensor array
483 consisting of BP for the detection of various ions, including Hg2+, Cd2+, and Pb2+ (Li,
484 Zhang, Wu, Cao, & Wu, 2018). By functionalizing the surface of BP, it became reactive
485 to specific metal ions, changing its electrical properties. Such changes were accurately
486 detected by BP sensor arrays, allowing for sensitive detection of metal ions. In addition,
487 strain induced bandgap modulation of BP, leading to a piezoresistive effect. This effect
488 manifested as significant changes in conductivity during mechanical deformation. The
489 array exhibited excellent mechanical flexibility and stability, withstanding a strain limit
490 of 1% and maintaining stability after 500 bending cycles. These features allowed the
491 sensor to maintain excellent performance under mechanical stresses, highlighting its
492 sensitivity and selectivity.
493 4.5 Other food chemical pollutants
494 Bisphenol A (BPA). Commonly used in plastics and resins manufacturing, BPA
495 poses a health risk by entering the human body through contaminated food. Shen et al.
496 exploited stable Gr@BP nanocomposites for photoelectrochemical (PEC) sensing of
497 BPA, using a solvothermal method (Shen, Liu, Wu, & Yang, 2022). The innovation in
498 this study was the in situ growth of BP on the Gr surface, using RP as a cost-effective
499 and accessible precursor. This facile solvothermal approach effectively created strong
500 covalent bonds between BP and Gr, ensuring uniform and thorough integration of BP
501 onto Gr. Gr's extensive surface area and superior electrical conductivity significantly
502 enhanced the sensor's performance. Additionally, BP's variable bandgap and high
503 carrier mobility endowed the nanocomposites with unique properties. The combination
22
504 of Gr and BP greatly improved the stability, conductivity, and photoelectrochemical
505 properties of the nanocomposites, leading to increased sensitivity, selectivity, and
506 stability in BPA detection. Remarkably, the study foundthat the photocurrent
507 maintained over 92% of its initial value after 29 d, demonstrating the significant
508 synergistic effect between Gr and BP in enhancing the PEC sensor.
509
510 Fig. 4. Schematic of BP applications on food safety. A. BP-GO composites modifying the electrode
511 for ZEN detection (Hu et al., 2022a). B. PET sensor using MC adsorbed on the surface of Ag+-
512 modified BP for TC detection (Chen et al., 2021). C. LFIS LFIS incorporating the excellent
513 photothermal characteristics of BP for NOR detection (Ren et al., 2021). D. Obtained BP-Pt
23
514 nanomaterials, including TEM (inset: HRTEM and Fourier diffractogram images), AFM images,
515 and the comparisons of the peroxidase-like performance of PtNPs, BP-Pt (with AA), and BP-Pt
516 (without AA) (Li et al., 2021b). E. Electrochemical sensor using BP co-decorated with poly
517 PEDOTNPs and S-β-CD for CLB and RAC detection (Ge et al., 2019). F. Portable wireless
518 intelligent sensor based on Ti3C2-MXene/BP nanohybrids for NAA detection (Zhu et al., 2021).
519 5. Conclusions and outlook
520 Sensors based on a range of nanomaterials has been widely applied in the field of
521 food safety monitoring. Among them, BP with its exceptional physical and chemical
522 properties, has demonstrated a variety of functions in this area. This review provides
523 an overview of the current applications of BP in detecting various chemical
524 contaminants in food. As shown in Table 2, the multifunctionality of BP is primarily
525 manifested in the following aspects: 1. modifying electrodes to enhance electrical
526 conductivity and strengthen electrochemical signals; serving as a carrier material to
527 effectively immobilize signal molecules or target recognition units; 3. embodying
528 nanozyme-like activities, which can replace biological enzymes for direct or indirect
529 detection of target contaminants; 4. affecting the optical absorption, luminescence, and
530 nonlinear optical properties of excitons; 5. possessing excellent thermal properties,
531 which can be combined with other signal detection modes to construct multimodal
532 sensors, thereby improving the accuracy and reliability of detection; 6. exhibiting both
533 sensitive mechanical strain properties and outstanding mechanical stability, making it
534 suitable for the development of flexible sensors. Therefore, as a nanomaterial that has
535 garnered considerable attention, BP has attracted the interest of many researchers, and
536 its potential for application is immense.
537 However, compared to traditional 2D nanomaterials, research on BP is still in its
538 nascent stage and faces several critical challenges. Firstly, existing synthesis methods
539 have not yet achieved large-scale, high-quality production of BP. The commonly used
24
540 top-down synthesis approaches lack morphological control and reproducibility. PLD
541 has been successfully employed to synthesize centimeter-scale BP on mica substrates,
542 which is one of the highly promising method. But further research is required to achieve
543 wafer-scale production. The developed methods should facilitate the transfer of BP into
544 different substrates or solvents while allowing control over the number and shape of BP
545 layers through the adjustment of experimental parameters. Since the properties of BP
546 are closely related to its layer count and shape, controllable preparation methods are
547 essential for developing BP with superior characteristics. Secondly, the instability of
548 BP can affect its performance and applications. Although current strategies include
549 isolating electron lone pairs and using physical or chemical methods to adjust the
550 bandgap, additional protective measures might impact its sensitivity and selectivity.
551 VdW heterojunctions appear to offer a potential solution. Theoretically, nanomaterials
552 with no suspended bond surfaces can be integrated with BP without the need for lattice
553 matching or processing compatibility. VdW heterojunctions preserve the structural
554 properties of the original components and produce synergistic effects due to weak
555 interactions in the hybrid system. Moreover, their tunable bandgap and high carrier
556 mobility enhance the construction of twisted heterostructures based on different layers
557 of BP, achieving more precise integration of various materials. Thirdly, the current BP-
558 based nanomaterial methods for food safety analysis reported in the literature mainly
559 target one or two substances and are not yet capable of simultaneously detecting
560 multiple substances. The introduction of multiplexing techniques, such as parallel
561 detection of micro- or nano-arrays, or other concepts like DNA circuits, could promote
562 efficient multi-target analysis. Fourthly, strong anti-interference measures are required
563 because food samples contain substantial amounts of diverse and complex matrix
564 components. Simple analytical methods that reduce or eliminate matrix effects can
25
565 further improve the applicability of BP-based nanomaterial construction equipment.
566 In summary, BP has shown its immense value in the application of food safety.
567 With the rapid development of BP in the fields of nanomaterial science and food safety
568 science, more captivating properties and functionalities of BP are expected to be further
569 explored and applied. This will greatly contribute to the development of the food safety
570 field.
26
571 Table 2. Application of BP-based nanomaterials in the detection of food contamination.
Targets Materials Material properties utilized Detection methods Liner range LODs Sample types Ref.
Toxins
OTA BP-Ag electrode modification, conductivity electrochemical sensor 0.3~10 μg/mL 0.18 μg/mL beer, grape juice (Xiang et al., 2018)
AFB1 0.02 ng/mL
BP-AuNP carrier of aptamer, conductivity paper-based aptasensor 0.05~10 ng/mL wine (Jiang et al., 2022)
OTA 0.04 ng/mL
OTA BP-carbon dot carrier of aptamer, conductivity aptasensor 0.1fg/mL ~10 ng/mL 0.03 fg/mL wheat, grape juice (Li et al., 2021a)
ZEN BP-AuNP carrier of Ab, fluorescence quenching FICS — 0.1 μg/L cereal (Li et al., 2020)
carriers of signal molecular and MIP, internal reference
ZEN BP-GO 0.05~13 μM 12.7 nM human serum (Hu et al., 2022)
electrocatalysis electrochemical sensor
PAT BP-AuNP carrier of aptamer, conductivity aptasensor 0.1 nM ~10.0 μM 0.03 nM apple juice (Xu et al., 2019)
OTA, PAT BP-AuNP carriers of aptamer, conductivity aptasensor 0.1 pg/mL~ 0.1μg/mL — apple juice (Zhao et al., 2021)
(Ramalingam et al.,
OA BP-AuNP carrier of aptamer, conductivity microfluidic aptasensor 10~ 250 nM 8 pM mussel
2019)
AFB1 BP-UCNP fluorescence quenching UCNPs aptasensor 0.2~500 ng/mL 0.03 ng/mL peanut oil, wheat (Wu et al., 2021)
BP/MWCNTs-
AFB1 carrier of nanobody, electrocatalysis immunosensor 1.0 pM ~ 5.0 nM 0.27 pM tea, rice (Zhang et al., 2022)
COOH
carrier of Ab, immunochromatographic
DON BP-Au 1~106 pg/mL 0.15 pg/mL maize, oat, millet (Zhou et al., 2023)
colorimetric/photothermal reagents sensor
PAT BP-AuNP carriers of aptamer, conductivity aptasensor 0.1 nM~100.0 µM 0.043 nM apple, pear, tomato (Xu et al., 2023)
Veterinary drugs
TC BPAg(+)/MC sensing FET 10 nM~1 μM 7.94 nM — (Chen et al., 2023)
NOR BP colorimetric/photothermal reagents LFIS — 45 pg/mL tap water, river (Ren et al., 2021)
tap water, milk,
NOR BP-AuNP carrier of MIP, electrocatalysis electrochemical sensor 0.1 nM~10 μM 0.012 nM (Li et al., 2022)
soil
NISA 0.01~10 μg/L 0.005 μg/L fish, beef, chicken,
ENR BP-Pt carrier of Ab, nanoenzyme (Li et al., 2021b)
PT-NISA — 0.008 μg/L eggs
PEF BP-AuNP carrier of MIP, conductivity electrochemical sensor 0.005~10μM 0.80 nM milk, orange juice (Li et al., 2024)
CLB BP-Nf (IP) electrode modification, conductivity electrochemical sensor 0.06~24 μM 3.7 nM beef, serum (Ge et al., 2018)
RAC S-b-CD- conductivity, electrocatalysis, host electrochemical sensor 0.3~ 9.4 μM 0.14 μM beef, feed, serum (Ge et al., 2019)
27
CLB PEDOTNP/BP recognition 0.3~ 90 μM 0.12 μM
MG BP-cysteine-AuNP carrier of aptamer, conductivity interdigital electrode sensor 1.0~1.0×104 ng/L 0.3 ng/L — (Wu et al., 2020)
bottled water, milk,
DES BP-AuNP signal indicator, carrier of Ab PT-Chip sensor 0.5~50 μg/L 0.1 μg/L (Wang et al., 2023)
beef
milk, beef, fish,
DES PDA/BP carrier of Ab, fluorescence quenching fluorometric immunosensor 0.1~1000 ng/mL 83 pg/mL (Ren et al., 2018)
urine
0.3~20 ng/mL
colorimetric and photo- (colorimetric)
DES BP-AuNP carrier of Ab, nanoenzyme 0.08 ng/mL milk, tap water (Ding et al., 2021)
thermal dualmode NISA 0.08~20 ng/mL
(photothermal)
water, milk, milk
E2 BP-AuNP photothermal signal PT-LFIS — 50 pg/mL (Zhang et al., 2023)
powder
E2 BP photothermal effect PT-immunofiltration strip — 0.1 ng/mL water, milk (Lu et al., 2019)
water, food, serum,
E2 BP-Au/UCNP carrier of Ab, fluorescence quenching UCNPs aptasensor 0.1~100 ng/mL 92 pg/mL (Ren et al., 2019)
urine
Pesticide Residues
portable wireless intelligent
NAA Ti3C2-MXene/BP nanozyme 0.02~40 μM 1.6 nM oil, water (Zhu et al., 2021)
sensor
portable sensor with ML
ML HNT/BP-AgNP conductivity 0.7~55 μM 0.3 μM potato, carrot (Ge et al., 2023)
model and LS-SVM
BP@MWCNTs- lake, tap water,
CD electrode modification, conductivity electrochemical sensor 9.0~1000 nM 4.0 nM (Liao et al., 2023)
COOH pear
PQ 0.18 ng/mL
BP-UCNP carrier of aptamer, fluorescence burst FRET biosensor 1.0~1.0 × 105 ng/mL tea, matcha powder (Wang et al., 2022)
CD 0.45 ng/mL
hBP/TH/PLL- electrode modification, carrier of
ACE electrochemical sensor 10 fM~1 μM 9.41 fM tea (Ma et al., 2023)
AuNP aptamer
lake, soil, cabbage,
MH hBP/PLL/AuNP carrier of aptamer, conductivity aptasensor 0.1 pM~1 µM 2.81 fM (Ma et al., 2023)
greengrocery
MP PLL-BP/AuNP carrier of aptamer, conductivity aptasensor 1~105 pM 0.49 pM water (Guo et al., 2023)
Heavy Metal
Hg2+ BP sensing FET sensor — 0.01 ppb water (Li et al., 2017)
carrier of aptamer, electrode (Wang et al.,
Pb2+ BP ECL sensor 0.5 × 10− 3 ~5 nM 0.27 pM water
modification 2021b)
As BP/AuNP/DTT sensing FET sensor — 1 nM water (Zhou et al., 2018)
Hg2+, Cd2+,
BP strain-sensitivity FIBA — 1 μg/L tap water (Li et al., 2018)
Pb2+
28
Pb2+ BP-TFG optical tunable features fiber optic chemical sensor 0.1~1.5×107 ppb 0.25 ppb water (Liu et al., 2018)
Pb2+, Cd2+, 1, 3,10,1
BP sensing ion sensor — water (Li et al., 2015)
AsO2-,Hg2+ ppb
Others
BPA Gr@BP conductivity, light absorption ability PEC sensor 0.01~1000 nM 0.003 nM wastewater (Shen et al., 2022)
carrier of aptamer, molecular
fluorescent sensor with
BPA BP-HARF adsorption energy, transmittance, and — 1.69 pM blood, water (Qiao et al., 2020)
HARF
light confinement
plastic container,
BPA BP-PG electrode modification, conductivity electrochemical sensor 4×10−8~5.5×10−5 M 7.8×10−9 M (Cai et al., 2019b)
urine
water, oil, canned
BPA BP-AuNP carrier of Ab, NIR PT transduction PT-LFIS — 0.24 ng/mL (Ren et al., 2019)
yellow peach, milk
PCB77 BP (HA)-AuNP carrier of aptamer, conductivity aptasensor 100 pg/L~10 μg/L 33 pg/L tap water (Liang et al., 2019)
BP/AuNP/Ni-Fe (Prasanna et al.,
DPA conductivity, electrocatalysis electrochemical sensor 0.013~1003.8 μM 4.63 nM fruit
LDH 2024)
572 PDA: Polydopamine; hBP: hydroxylated BP; TH: thionine; MC: Melamine cyanurate; FICS: fluorescent immunochromatographic sensor; UCP: upconversion nanoparticles; PT: photothermal;
573 ECL: electrochemiluminescence; PEC: photoelectrochemical; FRET: fluorescence resonance energy transfer; ML: machine learning; LS-SVM: least squares support vector machine; FIBA:
574 flexible integrated BP sensor arrays; HARF: hollow core anti-resonant fiber; TFG: tilted fiber grating; LSP: localized surface plasmon; NIR: near-infrared. PCB77: 3,3’,4,4’-tetra chlorobiphenyl;
575 DPA: diphenylamine.
29
576 CRediT authorship contribution statement
577 Wei Han: Conceptualization, Writing–original draft, Writing–review & editing,
578 Investigation, Formal analysis. Peiyuan Wei: Visualization, Investigation. Lingling Xie:
579 Formal analysis, Investigation, Funding acquisition. Limin Zhu: Conceptualization,
580 Writing – review & editing, Funding acquisition. Baoshan He: Formal analysis,
581 Investigation. Xiaoyu Cao: Conceptualization, Validation, Resources, Writing – review
582 & editing, Supervision, Project administration, Funding acquisition.
583
584
585
586
587
588
589
590
591
592
593
594
595
30
596 Acknowledgments
597 This work was supported by Program for Innovative Team (in Science and
598 Technology) in University of Henan Province, China (No. 24IRTSTHN006), Natural
599 Science Foundation of Henan, China (Nos. 232300421080, 222300420138), Key
600 Scientific Research Programs in Universities of Henan Province, China–Special
601 Projects for Basic Research (No. 23ZX008), Science and Technology Project of Henan
602 Province, China (Nos. 232102241038, 232102241004), and Innovative Funds Plan of
603 Henan University of Technology, China (No. 2020ZKCJ04).
31
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Food Chemistry

Functional black phosphorus-based sensors for food safety applications: a review

Manuscript Number: FOODCHEM-D-24-01403

Article Type: Review Article

Keywords: Black phosphorus; Preparation; Function; Sensors; Food safety

 The latest progress on BP-based materials in food safety applications was

 BP remarkable versatility in applications was exhibited.

 The respective practicality, limitations, and challenges were discussed.

1 Functional black phosphorus-based sensors

2 for food safety applications: a review

4 Wei Han a, Peiyuan Wei a, Lingling Xie c, Limin Zhu a,*,

5 Baoshan He b,*, Xiaoyu Cao a,*

10 Zhengzhou, Henan 450001, PR China

12 Zhengzhou, Henan 450001, PR China

14 Henan 450001, PR China

20 * Corresponding author. E-mail address: [email protected] (X. Cao),

21 [email protected] (B. He), [email protected] (L. Zhu).

28 been employed to improve sensor performance. Particularly, black phosphorus (BP)

30 ultra-high charge mobility, easy surface functionalization, enhanced optical absorption,

34 comprehensively summarized. Moreover, challenges in BP’s preparation and stability

36 covering preparation, passivation, and applications. Through analysis of challenges and

40 Black phosphorus; Preparation; Function; Sensors; Food safety

54 convenient detection techniques for the quantitative assessments of food contaminants

57 challenges like laborious sample preparation, complex instrument operations, and

58 limited on-site screening capabilities. Sensor-based analytical methods, offering

59 advantages in terms of cost, sensitivity, and accuracy, present a promising solution to

61 Numerous nanomaterials have been extensively employed to improve the

63 Notably, black phosphorus (BP) is emerging as a single-element two-dimensional (2D)

65 structure and outstanding physicochemical properties, BP can perform various

68 structure distinct from conventional 2D materials. This structure can be employed to

76 conductance, resistance, and other photoelectric response parameters (Fig. 1B)

77 (Castellanos-Gomez, 2015). Compared to other 2D materials, BP exhibits a higher

78 extinction coefficient and photothermal conversion efficiency. It can be used to

85 providing excellent mechanical flexibility (Vaquero-Garzon, Frisenda, & Castellanos-

86 Gomez, 2019). Consequently, functional BP presents a viable option for constructing

88 contaminant identification in intricate food samples. Numerous studies have applied BP

91 food chemical contaminants. Furthermore, promoting practical applications of BP is

94 synthesizing BP with good crystallinity, reproducibility, and wafer scale are

95 unavailable. To date, considerable research has been devoted to producing high-quality

96 BP in a cost-effective manner and developing surface/interface-engineering-based

99 applications of this intriguing nanomaterial are still in their infancy.

104 based on the mechanical properties of BP (Vaquero-Garzon, 2019).

105 To address these issues, this review presents a state-of-the-art description of BP

112 critical and distinct nanomaterial in food safety assessments.

114 Scheme 1. BP preparation, passivation, and food safety applications.

124 2.1 Top-Down exfoliation

125 Conventional mechanical microcleavage is a scotch-tape-based exfoliation

127 substrate (Liu et al., 2014). Recently, numerous mechanical-exfoliation-based thinning

142 and lateral dimensions of 300 to 900 nm. In particular, in 1-buthyl-3-

143 methylimidazolium hexafluorophosphate ([BMIM]PF6), the yield increased to 28%

146 et al., 2017).

147 Electrochemical delamination utilizes electrolytes to stimulate ions in the solution

159 n-butylammonium acetate, which provided a new approach to producing BP with a

162 difficulty in controlling the edges.

163 2.2 Bottom-up assembly

164 In chemical vapor deposition (CVD), a precursor is evaporated and re-condensed

165 to form nanostructures on substrate surfaces in specific atmospheres at controlled

181 Wang, & Li, 2022).

194 2022). Generally, it involves an evaporation–condensation-driven solid–vapor–solid

5 Baoshan He b,, Xiaoyu Cao a,