Applied Surface Science 603 (2022) 154445

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Applied Surface Science

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Super-hydrophilic SERS sensor with both ultrahigh activity and exceptional

3D spatial uniformity for sensitive detection of toxic pollutants
Chang Wang a, Shihao Zhou b, Yue Tian a, Anxin Jiao a, Hui Ma a, Mengya Zhang a, Linqi Zheng c,
Xiangdong Liu a, Qingqiang Cui a, Shuang Li c, Ming Chen a, *
a
School of Physics, Shandong University, Jinan 250100, PR China
b
Department of Physics, University of California, Santa Barbara, CA 93106, USA
c
School of Science, Shandong Jianzhu University, Jinan 250101, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The powerful surface-enhanced Raman scattering spectroscopy (SERS) practical technique is not only related to
Super-hydrophilic SERS sensor signal enhancement but also heavily dependent on spatial uniformity. Different from the routine hydrophobic
Three-dimensional SERS uniformity substrates, an extraordinary super-hydrophilic SERS sensor is established by loading plasmonic Au nanoparticles
“Coffee ring” effect of colloidal analytes
(NPs) on two-dimensional (2D) hexagonal boron nitride (h-BN) then the hybrids uniformly are grafted into 3D
Ultrahigh SERS activity
Excellent flexibility
bacterial nanocelluloses (BNCs). The Au NPs@h-BN/BNCs exhibit a remarkably high SERS activity with a limit of
detection (LOD) of dyes at 0.1 femtomole (fM) level (~10-16 M). It is attributed to the strong synergistic coupling
effect between highly dense Au NPs and modified h-BN as well as multiple light-scattering effects in 3D porous
supports. More importantly, the distinctive advantage is further highlighted by the exceptional 3D spatial SERS
uniformity with relative standard deviation (RSD) less than 3.4% along both horizontal and vertical directions.
The unique feature is due to the 3D homogeneous distribution of the injected colloidal analytes via ultra-rapid
liquid diffusion throughout the entire body with superior wettability. Besides, the flexible SERS substrates with
excellent easy-tailorable mechanical properties can be robust enough to withstand the portable operations in
real-world scenarios. These competitive merits are particularly beneficial for reliable SERS quantitative
surveillance.

1. Introduction quantitative clinical biomolecular assessments [10,11] and point-of-

care (POC) diagnostics [6,12,13]. Recently, the robust SERS substrates
As one of the most promising analytical techniques, surface- with excellent Raman signal uniformity are also very important for the
enhanced Raman scattering spectroscopy (SERS) with enriched molec­ easy-to-use portable SERS operation with better laser misfocus-tolerant
ular “fingerprint” information has attracted increasingly tremendous feature [13,14], avoiding the tedious laser alignment prior to Raman
interest in the past decades [1–3]. As for ultrasensitive detection of detection. Therefore, the growing demand for practical SERS in real-
biological/chemical molecules, many efforts have been devoted to the world scenarios is not only related to the unparalleled activity but also
construction of efficient SERS nano-substrates by combining plasmonic heavily dependent on the exceptional spatial uniformity.
metals with band-gap semiconductors [3–6]. The SERS activity is related In order to improve SERS signal uniformity, the routine strategies
to the localized surface plasmon resonance (LSPR)-boosted electro­ have been mainly focused on the super-hydrophobic substrates with
magnetic (EM) enhancement and/or chemical enhancement (CE) via homogeneous horizontal (x-y) microstructures [9–11,15–19]. The poor
effective charge transfer (CT) between probe molecules and nano- signal homogeneity is usually caused by the uneven “coffee ring” pat­
substrates [4–8]. Besides, the reliable analysis of analytes is also terns of colloidal SERS nano-substrates during the drying process on
increasingly relied on excellent spatial SERS homogeneity that can truly silicon wafers or glass plates [20–28]. The ubiquitous “coffee ring”
reflect the chemical information of probe molecules absorbed on phenomenon of a dried droplet during spontaneous hydrodynamic
random sites of nano-substrates [9]. Especially, the uniform repeatable process originated from the enhanced evaporated rate at liquid edge. It
SERS signals over large spatial scales are highly desirable for enables the nonvolatile components to be redistributed and

* Corresponding author.
E-mail address: chenming@[Link] (M. Chen).

[Link]
Received 26 May 2022; Received in revised form 19 July 2022; Accepted 1 August 2022
Available online 2 August 2022
0169-4332/© 2022 Elsevier B.V. All rights reserved.
C. Wang et al. Applied Surface Science 603 (2022) 154445

concentrated at the perimeter region (ring-like residues) [20,22,23,25]. hexagonal boron nitride (h-BN) then the hybrids are uniformly grafted
To mitigate the “coffee ring” effect of SERS nano-substrates, many into 3D bacterial nano-celluloses (BNCs) supports. The detection limit of
physical lithographic techniques and/or chemical self-assembly strate­ dyes adsorbed on the Au NPs@h-BN/BNCs is achieved as low as ~ 10-16
gies have been developed for fabricating super-hydrophobic surface M (0.1 femtomole (fM)), facilitating the ultrasensitive detection of trace
structures. They are composed of photolithography [29], colloidal self- molecules. The unique advantage of this work is the unparalleled 3D
assembly [8,30], ordered templates [15,16,18,19,31–35], lith­ Raman signal homogeneity with relative standard deviation (RSD) less
graphy@plasma etching [17,36], femtosecond laser printing [7,37], than 3.4% at both centimeter-scale horizontal plane and micrometer-in-
holographic lithography [9], electron beam lithography (EBL) [38,39] depth vertical direction. It is mainly attributed to the ultra-rapid uni­
and focused ion beam (FIB) [40,41]. Compared to previous colloidal form-diffusion of the colloidal analytes throughout the super-
SERS nano-substrates with uneven “coffee ring” structures, these two- hydrophilic 3D body. On the other hand, the flexible SERS sensor with
dimensional (2D) well-ordered planes with intrinsic super- excellent easy-tailorable mechanical portability can be robust enough to
hydrophobicity provide higher homogeneous Raman signals. withstand the emerging portable SERS operations (Scheme 1). Besides, it
Nevertheless, the present hydrophobic 2D homogeneous planes are also possesses some additional competitive SERS merits of versatility,
still not sufficient for the progress of SERS from a promising state to a reproducibility, repeatability and multiplex detection distinguishability.
practical technique. The higher requirement for accurate SERS di­ These findings hold great promising potential for promoting practical
agnostics is further concentrated on the excellent 3D spatial SERS uni­ SERS applications.
formity throughout the entire substrates. The reason is that the “coffee
ring” pattern of colloidal analytes can also lead to the inhomogeneous 2. Experimental section
spatial Raman signals. Commonly, the Raman test is prepared by
dropping a drop of colloidal analytes on the substrates. As for nonvol­ 2.1. Chemicals
atile solutes, such as organic small molecules, biomacromolecules or
polymers [22–24], the “coffee ring” structures of colloidal analytes will Chloroauric acid (HAuCl4) was obtained from Sinopharm Chemical
be formed on the well-aligned hydrophobic planes. It will result in some Reagent Co., Ltd. Sodium hydroxide (NaOH), sodium sulfate (Na2SO4),
unpredictable Raman signal fluctuation and give rise to the uneven hexagonal boron nitride (h-BN) and N-VinyPyrrolidone (NVP) were
distribution of Raman signals over the large-scale areas of probe mole­ purchased from Macklin Chemistry Co., Ltd. The bacterial cellulose
cules. On the other hand, most of these hydrophobic microstructures are (BNCs) samples were purchased from Guanlan Technology limited
still restricted to the horizontal 2D uniformity, which are not suitable for corporation. Crystal violet (CV) molecules, anthracene molecules and
obtaining highly uniform Raman signals in vertical (z) in-depth direc­ pyrene molecules were purchased from Aladdin Chemistry Co., Ltd
tion. Because of the intrinsic poor hydrophilicity, the hydrophobic (Shanghai, China). Ethanol (C2H5OH) was purchased from Tianjin Fuyu
planes cannot enable the injected colloidal analytes to be uniformly Fine Chemical Co., Ltd. All the above chemicals were of reagent grade
immersed into the entire substrates in both horizontals (x-y) and vertical and used as received without further purification.
(z) in-depth direction. Thus, the disparate concentrations of dried probe
molecules along the z-direction will be frequently formed after the
colloidal analytes dropped on these non-hygroscopic microstructures. 2.2. Hydroxylation of h-BN nanosheets
The uneven distributions of probe molecules at different depths of SERS
substrate can also lead to the poor Raman signal homogeneity in vertical The functionalization of h-BN nanosheets was carried out as follows.
direction. Up to now, the realization of 3D spatial SERS homogeneity in Typically, 2.4 g NaOH was dissolved in 30 mL deionized water to pre­
all x-y-z directions among the entire substrates is still a great challenge. pare 2 M NaOH solution, and then added in 0.1 g h-BN. The suspended
Different from the routine hydrophobic substrates, we demonstrate solution was oscillated ultrasonically for 1 h. After the reaction, the
an extraordinary super-hydrophilic sensor that simultaneously possesses suspension was centrifuged at 10000 rpm for 10 min and washed with
both ultrahigh SERS activity and exceptional 3D spatial uniformity deionized water. This procedure was repeated several times until the pH
along horizontal and vertical directions. The unusual SERS flexible of the supernatant liquid was close to neutral. The hydroxylated h-BN
substrates can be constructed by immobilizing plasmonic Au NPs on 2D powder prepared was denoted as h-BN(–OH).

Scheme 1. Diagram of the fabrication of Au NPs@h-BN/BNCs SERS flexible sensors and ultrasensitive detection of mixed PAHs.

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2.3. Fabrication of Au NPs@h-BN hybrids hydroxy (–OH) groups formed on the hydroxylated h-BN, providing
enough reducing agents for redox reactions [42–44]. After light irradi­
The hybrid nanostructures were synthesized by xenon lamp irradi­ ation of 45 min, the microstructures of Au NPs@h-BN hybrids are
ation of h-BN(–OH) nanosheets in HAuCl4 solution. Typically, the illustrated by SEM and TEM images in Fig. 1. Compared to the original
mixture of 0.0032 g h-BN(–OH) powder, 5 mL NVP, and 0.9 mL ethanol lamelliform h-BN nanosheets with comparatively smooth surfaces
was stirred with a magnetic stirrer at 400 rpm for 1 h. And then 1.5 mL of (Fig. 1a and Figure S1, Supporting Information), highly dense and
0.005 M HAuCl4 was added into the above mixture and fully mixed monodisperse NPs can be detected on 2D surfaces (Fig. 1b). The size
through an ultrasonic oscillator. The suspension was then sealed with distribution in Fig. 1c reveals that the average size of these NPs is mainly
transparent membrane, irradiated by a laboratory xenon lamp (300 nm- located in the 28–33 nm region. Meanwhile, the dispersed distribution
1500 nm), and magnetically stirred at 200 rpm for 45 min. The nano­ of dense Au NPs formed on h-BN nanosheets is also verified by the TEM
products were centrifuged at 6000 rpm for 10 min and washed with image (Fig. 1d). Moreover, the detailed structural information of the
deionized water three times. cross region between an individual Au nanoparticle and h-BN nanosheet
is further intuitively revealed by high-resolution TEM (HRTEM)
2.4. Preparation of Au NPs@h-BN/BNCs (Fig. 1e). The lattice-spacing distances of 0.236 nm and 0.204 nm can be
attributed to Au (1 1 1) and (2 0 0) planes, whereas the peripheral crystal
20 mg as-prepared Au NPs@h-BN hybrids were diluted with 1 mL of fringe of 0.332 nm is consistent with h-BN (0 0 2) plane. Meanwhile, the
deionized water and added into 3.5 mL of 1 mg/mL BNCs gels. The metallic lattice fringes can be interconnected with the crystal fringes of
mixtures were mixed completely and uniformly by an electronic blender h-BN at the boundary region (Fig. 1e), implying the Au NPs are already
and then poured into a petri dish with a radius of 5 cm. The petri dish inserted in 2D supports. Based on the EDS pattern (Fig. 1f), the relative
was placed on the whirler at 120 rpm until the gels spread out uniformly atomic ratios of N, B and Au elements are calculated at about 51.3%,
inside the vessel. Finally, the mixtures were placed into the vacuum 47.0% and 1.7%, respectively. Then, the large-scale homogeneous dis­
dryer at 50 ℃ for 48 h and dehydrated into a membrane. Other mem­ tributions of Au, B and N elements can be further confirmed by the
branes containing various amounts of Au NPs@h-BN nanocomposites corresponding elemental mappings (Fig. 1g). It is concluded that the
(NCs) (5 mg, 10 mg, 25 mg) were prepared in the same procedures. highly dense and monodisperse plasmonic Au NPs can be successfully
generated on 2D h-BN nanosheets by an ease-operate photochemical
2.5. SERS measurements overgrowth strategy. The amount of Au NPs is dependent on the
photochemical reaction time, which gradually increases with prolonged
All SERS signals were collected by a confocal microprobe Raman light irradiation time (0–45 min) (Figure S2, Supporting Information).
spectrometer (Renishaw Raman spectroscopy) to compare SERS per­ The absorption spectra reveal that the LSPR peak intensity of plasmonic
formances of different nanostructures. All of the SERS spectra were Au NPs at ~ 520 nm becomes higher with increasing reaction time
collected at room temperature using the excitation wavelength 633 nm (Figure S3, Supporting Information). However, the excess irradiation
laser with an output power of 1 mW as well as the acquisition time of 1 s. time (>45 min) in this work will also enable many NPs to be inter­
In a typical Raman spectroscopic analysis, 10 µL analyte solutions were connected with each other and hinge-joined together, which are un­
separately added into a series of different SERS substrates and then dried suitable for providing monodisperse SERS active sites (Figure S4,
spontaneously for 6 h before Raman measurements. Supporting Information). Meanwhile, we found that the overgrowth
progress was suppressed by single-wavelength light irradiation and
2.6. Materials characterization some scattered irregular Au nanostructures were formed after a 60 min
reaction (Figure S5, Supporting Information). The adopted xenon lamp
The morphologies and chemical compositions of nanoproducts were source with broadband light in the range of 350 nm ~ 1500 nm can
characterized by focused ion beam electron microscope (FIB, Helios G4 provide double effects for improving photochemical overgrowth. The
UC) and transmission electron microscopy (TEM, JEOL-JEM-2100F) shorter wavelength light with higher photon energy is beneficial for the
equipped with an energy dispersive X-ray (EDX) spectroscopy via a photonic excitation of h-BN nanosheets. Moreover, the longer wave­
scanning transmission electron microscopy (STEM) unit. The contact length light induced thermal energy is also reutilized for heat-
angles of different samples were tested by DSA 100. The surface com­ accelerating photochemical liquid-reaction.
positions and element valence information were taken from X-ray Then, the construction of Au NPs@h-BN/BNCs flexible 3D nano­
photoelectron spectra (XPS) by a PHI Quantera SXM. The crystalline composites can be performed by grafting as-prepared Au NPs@h-BN
properties of nanoproducts were investigated by X-ray diffraction (XRD) hybrids into colloidal BNCs-based 3D supports. The photograph image
patterns (Rigaku, Smart Lab 9 kW). The absorption spectra were carried at the top region in Fig. 2a reveals the milk white color of initial BNCs.
out via a UV–visible–NIR spectrometer (20/30 PVTM Microspectropho­ Subsequently, the obtained four groups of Au NPs@h-BN/BNCs with the
tometer). Photoluminescence (PL) spectra were measured using a high- increased dosages (5–25 mg) of Au NP@h-BN hybrids are shown in
efficiency integrated fluorescence spectrometer (Hitachi F-4500) with Fig. 2a. The colloidal color of Au NPs@h-BN/BNCs becomes darker
an excitation wavelength of 350 nm. The Fourier transformed infrared purple with an increase of Au NP@h-BN hybrids (5–25 mg). As shown in
spectrums (FTIR) of nanoproducts were measured by a UV–visible-NIR Fig. 2b-c, the SEM and TEM images reveal that the bare BNCs are mainly
spectrometer (Bruker, ALPHA-T). All the photoelectrochemical mea­ composed of plentiful interconnected nanofibers with an average
surements were examined by using a standard three-electrode system diameter of about 30–50 nm. Moreover, abundant opening-porous
with 0.1 M Na2SO4 electrolyte solution on a CHI 760E electrochemical structures with the sizes changed from a few tens to hundreds of nano­
workstation (Shanghai Chenhua Instrumental Co., Ltd, China). The meters can be also clearly detected among 3D frameworks (Fig. 2c). As
photocurrent responses of the samples via 633 nm (500 mW) laser on or for the BNCs supports decorated with 20 mg Au NPs@h-BN hybrids, the
off were measured at 0.0 V. cross-sectional SEM views illustrate that the multilayer structures can be
stacked with each other after the drying procedure (Fig. 2d-e). The
2.7. Results and discussion corresponding thickness is measured at about 3.04 µm in Fig. 2e.
Although a few nano-pores among BNCs would be inevitably blocked by
The as-prepared Au NPs@h-BN hybrids were produced by photo­ inserting Au NPs@h-BN hybrids, there are also many residual nano-
chemical overgrowth of plasmonic NPs on 2D plates via xenon lamp channels that can be retained in the 3D body. It will give rise to the
light irradiation of h-BN precursors in HAuCl4 solution. The mechanism effective liquid diffusion and penetration of colloidal analytes in the
is dependent on the high-energy photon excitation of oxygen-containing subsequent SERS applications. Moreover, the 3D BNCs grafted with Au

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Fig. 1. SEM images of a) original h-BN nanosheets and b) as-prepared Au NPs@h-BN hybrids by xenon lamp light irradiation of h-BN precursors in HAuCl4 solution
for 45 min. c) The size distribution of monodispersed Au NPs on h-BN. d) TEM image of Au NPs@h-BN hybrids and e) HRTEM image of the cross region between an
individual Au nanoparticle and h-BN. f) The EDS pattern and g) elemental mapping results of Au NPs@h-BN hybrids.

Fig. 2. a) The photograph image of initial colloidal BNCs and four samples of Au NPs@h-BN/BNCs, from the top to down: the 3.5 mL of BNCs (1 mg/mL) decorated
with different dosages (5, 10, 15, 25 mg) of Au NPs@h-BN hybrids. b) SEM and c) TEM images of bare BNCs. d)-e) The cross-sectional SEM views of the Au NPs@h-
BN/BNCs composed of 20 mg Au NPs@h-BN hybrids, f) the top SEM view and g)- h) TEM and elemental mapping images of the nanoproducts.

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NPs@h-BN hybrids can be further verified by the SEM and TEM images weaker peak at 190.7 eV is related to the B-O band (Fig. 4a). As for Au
(Fig. 2f-g), implying the 0D@2D hybrids can be successfully immobi­ NPs@h-BN hybrids, besides the above two peaks, an additional XPS
lized in 3D frameworks. Then, the elemental mapping images of the peak located at 189.9 eV should be derived from the contact of B and Au,
obtained Au NPs@h-BN/BNCs are illustrated in Fig. 2h. The C element which has been verified in the recent study [46]. It implies the formation
originating from BNCs can be found throughout the whole support, and of chemical band between B and Au in this work, supporting the over­
lamelliform-shaped distributions of B and N elements are derived from growth of Au NPs on h-BN nanosheets, instead of physical mixture of
h-BN nanosheets. Meanwhile, the dispersed distribution of Au NPs two separate components. On the other hand, the XPS peak of N 1s
clearly reveals the monodisperse plasmonic metallic NPs formed on 2D originating from Au NPs@h-BN hybrids is located at ~ 396.8 eV, which
nanoplates. is slightly negative-shifted 0.2 eV in comparison with bare h-BN
In addition, the crystallographic phases and optical absorption (Fig. 4b). The negative shift of N 1s verifies the modified electronic
properties of the obtained Au NPs@h-BN/BNCs and reference samples structures of h-BN after decorating plasmonic Au NPs. Moreover, the
including Au NPs@h-BN hybrids, original h-BN and BNCs were inves­ time-dependent photocurrent responses of as-prepared Au NPs@h-BN
tigated by XRD and absorption spectra tests. As shown in Fig. 3a, the hybrids and bare h-BN nanosheets were performed by 633 nm laser
three diffraction peaks of bare BNCs at about 14.4◦ , 16.6◦ and 22.6◦ can excitations (Fig. 4c). Clearly, the Au NPs@h-BN hybrids exhibit a much
be indexed to (1 0 1), (1 1 1) and (0 0 2) planes (JCPDS#03-0829) [45]. higher photocurrent density, which is already ~ 5 times higher than that
As for original h-BN nanosheets, a series of diffraction peaks at about of bare h-BN nanosheets. The higher photocurrent response usually
26.9◦ , 41.8◦ , 44.1◦ , 50.2◦ , 55.1◦ and 76.2◦ are attributed to the (0 0 2), implies higher efficient migration of photon-excited charge carriers
(1 0 0), (1 0 1), (1 0 2), (0 0 4) and (1 1 0) planes (JCPDS#73-2095) [46]. [49]. In this way, the tightly linked hybrids have a great ability to
After overgrowth of Au NPs on h-BN nanosheets, the diffraction peak at accelerate the transmission of photon-triggered electrons. Meanwhile,
38.5◦ that originated from Au (1 1 1) plane (JCPDS#04-0784) can be the enhanced separation of photon-excited electron-hole pairs on the
observed on as-prepared Au NPs@h-BN hybrids. Then, the obtained Au modified h-BN can be also verified by PL spectra (Fig. 4d). The PL in­
NPs@h-BN/BNCs exhibit some co-existence XRD diffraction peaks tensity would be mainly derived from energy emission during the
derived from 0D Au NPs and 2D h-BN as well as 3D BNCs. On the other recombination of photon-excited electrons and holes on h-BN semi­
hand, the absorption spectra of bare 2D h-BN nanosheets or 3D BNCs conductors [50,51]. As for Au NPs@h-BN hybrids, the PL intensity is
support shows a very weak absorbance capacity in the visible-near much lower than that of original h-BN nanosheets. Thus, the recombi­
infrared (NIR) light region of 400–1100 nm (Fig. 3b). After decorating nation of photo-induced charge carriers on semiconductors can be
with Au NPs, the as-prepared Au NPs@h-BN hybrids exhibit a new broad effectively suppressed by doping plasmonic Au NPs. Therefore, the as-
absorption peak at approximately 520 nm in Fig. 3b. It is related to the prepared Au NPs@h-BN hybrids with strong synergistic coupling ef­
LSPR property of dipole resonance oscillation of plasmonic nano­ fects possess an enhanced photo-induced carrier transfer (PICT) effi­
structures [42]. Finally, the obtained Au NPs@h-BN/BNCs show a pro­ ciency. It is expected to promote SERS activity in this work.
found increase in visible-NIR light absorbance capacity (Fig. 3b), in Based on the as-prepared binary Au NPs@h-BN hybrids and then
comparison with that of the three references. ternary Au NPs@h-BN/BNCs, the SERS performances were evaluated in
Meanwhile, in order to reveal the synergistic coupling effect between this work. Firstly, the enhanced SERS activity was illustrated by
plasmonic Au NPs and semiconductor h-BN in Au NPs@h-BN hybrids, adjusting the amount of Au NPs in as-prepared Au NPs@h-BN hybrids.
the XPS measurements were carried out in this work (Fig. 4a-b and The Raman spectra of CV molecules absorbed on the four samples of Au
Figure S6a-b in Supporting Information). Compared with initial h-BN, NPs@h-BN with Au compositions of 0–5.5% are displayed in Figure S7a
the survey XPS spectra (Figure S6a, Supporting Information) reveal the (Supporting information). Compared to other references, a remarkably
co-existence of B, N and Au elements on the surface of nano-hybrids. stronger Raman signal can be detected on the Au NPs@h-BN hybrids
Besides, the O 1s peak at about 531.5 eV originated from the adsorbed with Au composition of 1.7%. It is further confirmed by the variation of
O impurities in air, which is consistent with the previous works [47,48]. Raman peak intensity at 1617 cm− 1 as a function of different Au com­
The doublet features of Au 4f at ~83.6 eV and 87.5 eV are related to the positions (Figure S7b, Supporting Information). The increased SERS
binding energies of Au 4f7/2 and Au 4f5/2 (Figure S6b, Supporting In­ activity is attributed to the higher dense and dispersed Au NPs formed on
formation). It reveals the metallic states of Au0 formed in the hybrid 2D nanosheets. Compared to the insufficient candidates with fewer Au
structures [46]. Then, the enlarged XPS results of B 1s and N 1s (Fig. 4a- NPs, the enough monodisperse Au NPs can effectively improve EM
b) show that the electronic structures of B and N can be also modified by enhancement by the formation of enormous plasmonic SERS active sites.
doping plasmonic Au NPs on h-BN nanosheets. The XPS pattern of B 1 s Meanwhile, the CE contribution would be also improved by stronger
originating from initial h-BN nanosheets can be divided into two peaks: synergistic effects between plentiful metallic NPs and semiconductor
the stronger peak at 190.2 eV is attributed to the B-N bond and the nanoplates. However, the excess amount of Au NPs generated on h-BN,

Fig. 3. a) XRD results and b) absorption spectra of the obtained Au NPs@h-BN/BNCs, as-prepared Au NPs@h-BN hybrids, original h-BN nanosheets and initial
3D BNCs.

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Fig. 4. High-resolution XPS spectra of a) B 1 s and b) N 1 s originated from original h-BN and as-prepared Au NPs@h-BN hybrids. c) The photocurrent responses and
d) PL spectra of bare h-BN and Au NPs@h-BN hybrids.

such as ~5.5% Au NPs result in some suppressed SERS activity (Figure appropriate 1.7% Au composition were selected for the subsequent ex­
S7b, Supporting Information), due to the agglomerated plasmonic NPs periments. Then, based on the Raman spectra of CV molecules with
formed on 2D nanoplates [46]. Thus, the Au NPs@h-BN hybrids with different concentrations (Figure S7c, Supporting Information), the limit

Fig. 5. a) The Raman spectra of 10-6 M CV mol­

ecules absorbed on four nano-substrates,
including initial 3D BNCs and three groups of
Au NPs@h-BN/BNCs with 5, 10, and 20 mg dos­
ages of Au NPs@h-BN hybrids, respectively, b)
the variations of Raman peak intensities of CV
molecules at 1617 and 1173 cm− 1 versus four
different samples, c) the Raman spectra of CV
molecules with different concentrations (10-6 ~
10-16 M) absorbed on Au NPs@h-BN/BNCs with
20 mg dosages of Au NPs@h-BN hybrids, d) the
variations of Raman peak intensities at 1617 and
1173 cm− 1 versus the logarithm concentrations
of CV molecules.

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of detection (LOD) is calculated about 10-14 M. Meanwhile, the linear NPs@h-BN/BNCs should be highly related to the remarkably strong
relationships between Raman peak intensities and molecular concen­ light absorbance capacity (Fig. 3). Meanwhile, 3D porous BNCs supports
trations are also illustrated in Figure S7d (Supporting Information). As with plentiful opening nano-channels (Fig. 2) possess an enhanced
for ternary Au NPs@h-BN/BNCs, the SERS activity is not only related to multiple light-scattering effect during long optical paths that enables
the proper amount of Au NPs on h-BN, but also dependent on the dosage more photons to be effectively trapped in SERS substrates. The above
of Au NPs@h-BN hybrids that grafted into 3D BNCs. In this way, the double factors give rise to the high-efficiency conversion and utilization
Raman spectra of CV molecules absorbed on the four samples are shown of incident light for promoting SERS activity. On the other hand, we also
in Fig. 5a. The four groups of SERS substrates are composed of original found that the excess dosage (>20 mg) of Au NPs@h-BN hybrids added
BNCs, three types of Au NPs@h-BN/BNCs with 5, 10, and 20 mg dosages into BNCs would result in some saturated SERS activity, thus there is no
of Au NPs@h-BN hybrids. It can be seen that the Raman signals per­ obvious increase in Raman signals. In this way, the ternary Au NPs@h-
formed on the Au NPs@h-BN/BNCs with 20 mg dosages of Au NPs@h- BN/BNCs with 20 mg dosage of Au NPs@h-BN hybrids were adopted as
BN hybrids are significantly higher than that of the other three refer­ the optimal SERS substrates in this work. Then, the Raman spectra of CV
ences. The enhanced SERS activity is also intuitively confirmed by the molecules with different concentrations are in Fig. 5c-d. The dominant
variations of Raman peak intensities at 1617 and 1173 cm− 1 versus four characteristic bands can be distinguishable even if the molecular con­
different samples (Fig. 5b). For instance, the Raman peak intensity at centration sharply decreases to 10-16 M, approaching ultra-trace level at
1617 cm− 1 on the optimal Au NPs@h-BN/BNCs is about 9.3 and 3.5 0.1 femtomole (fM). The ultralow LOD is already two orders of magni­
times higher than that of bare BNCs (Fig. 5b) and binary Au NPs@h-BN tude better than that of Au NPs@h-BN hybrids (Figure S7c, Supporting
hybrids (Figure S7b, Supporting Information). Compared to the binary Information), and also superior to many previous works (Table S1,
Au NPs@h-BN hybrids, the maximized SERS activity of ternary Au Supporting Information). On the other hand, based on the Raman peak

Fig. 6. The contact angle images after dropping a droplet of aqueous analytes (20 µL of 10-6 M CV molecules) for different time a-d) super-hydrophilic Au NPs@h-
BN/BNCs and e-h) reference Au NPs@h-BN hybrids dried on rigid Si plate, i-l) The excellent flexibility of the obtained Au NPs@h-BN/BNCs under different bending
conditions: rolled, twisted, folded, and scrunched, respectively, m-n) the easy-tailorable mechanical property and portability of the flexible SERS sensors.

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intensities of CV molecules at 1617 cm− 1, the enhancement factor (EF) reveal that abundant oxygen-rich functional groups (–OH, –COOH, and
value of the established SERS substrate is calculated to be about 1.07 × -C-O-C, etc.) can be detected on the Au NPs@h-BN/BNCs (Figure S9,
107 (detail in Figure S8, Supporting Information). Moreover, the well- Supporting Information). These hydrophilic groups that have been
defined linear responses of Raman peak intensities versus broad mo­ verified in the previous study [45], would also play an important role in
lecular concentrations (10-6 ~ 10-16 M) are shown in Fig. 5d. The this work. On the other hand, the mechanical flexibility of the obtained
experimental results facilitate ultrasensitive monitoring of extremely SERS substrates is also very important for practical applications. We
low dyes in some specific applications. Therefore, the ultrahigh SERS tested different bending conditions of the flexible Au NPs@h-BN/BNCs
activity of the obtained Au NPs@h-BN/BNCs can be sufficiently verified (Fig. 6i-l), which can be effectively rolled, twisted, folded, and
by the above comparative analyses. scrunched with no obvious damage to the main structure. The bending
Besides the ultrahigh SERS activity, the distinctive superiority of the experiments reveal the high flexibility of Au NPs@h-BN/BNCs in this
obtained Au NPs@h-BN/BNCs can be highlighted in terms of excep­ work. Moreover, the flexible nanoproducts can be further easily tailored
tional 3D spatial SERS uniformity. The unique merit is strongly depen­ into random strips (Fig. 6m-n), giving rise to the batch-production of
dent on the high wettability of super-hydrophilic SERS substrate, which portable SERS sensors with designated shapes.
is intuitively verified by the contract angle images after dropping a In order to evaluate the 3D spatial SERS uniformity of the obtained
droplet of aqueous CV analytes (Fig. 6a-d). Indeed, the contact angle of Au NPs@h-BN/BNCs, the 2D Raman signal homogeneity at the hori­
this droplet is measured at about 28◦ after keeping it for 0.02 s, which zontal (x-y) planar surface was firstly illustrated in this work. Based on
rapidly decreases to 14◦ at 0.06 s (Fig. 6a-c). Immediately, the liquid the different random points on the large area of Au NPs@h-BN/BNCs
droplet sharply penetrates into the super-hydrophilic 3D body, then (Fig. 7a), the ten groups of Raman spectra of 10-11 M CV molecules
instantly and completely infiltrates into the whole SERS substrate within are shown in Fig. 7b. Clearly, the Raman signals of probe molecules can
only ~1.76 s (Fig. 6d). The ultra-rapid liquid diffusion is beneficial for be well repeated at random points on large-scale planar surfaces. Then,
mitigating the droplet-induced “coffee-ring” pattern of colloidal analy­ the variations of Raman peak intensities at 1617 and 1173 cm− 1 versus
tes and facilitating the homogeneous distribution of probe molecules. different 10 points are illustrated in Fig. 7c. The corresponding RSD
For comparison, we also tested the liquid diffusion in the presence of values of two groups are calculated at about 2.13% and 3.35%,
bare Au NPs@h-BN hybrids dried on a rigid Si plate (Fig. 6e-h). It can be respectively, supporting the random point-to-point SERS uniformity at
seen that the contact angle of 63◦ at 0.02 s slightly changes to ~ 59◦ even the centimeter (cm) scale-planar surface. Besides, the plane-scanning
after keeping it for 600 s. The comparative experiments clearly confirm SERS tests were also separately performed on different enlarged re­
that the obtained Au NPs@h-BN/BNCs definitely possess an excellent gions. The mapping diagrams of Raman peak intensities at 1617 and
wettability for ultra-rapid diffusion and penetration of liquid droplets 1173 cm− 1 at micro-scale and even nano-scale areas are displayed in
throughout the 3D body. The corresponding mechanism is attributed to Fig. 7d. Based on the Raman scanning models with two steps of 1 µm and
the plentiful opening nano-pores and enough nano-channels formed 0.1 µm, the spatial discrete distributions of the Raman peak intensities
among 3D BNCs-based frameworks (Fig. 2). Moreover, the FTIR spectra with RSD values in the range of 2.57%~3.09% are shown in Fig. 7e. It

Fig. 7. a-b) Based on the obtained Au NPs@h-BN/BNCs, the Raman spectra of 10-11 M CV molecules recorded at different 10 random points on large-scale surface, c)
the variations of Raman peak intensities at 1617 and 1173 cm− 1 versus different 10 points, d) the micro-scale and nano-scale mapping diagrams of Raman peak
intensities at 1617 and 1173 cm− 1 performed on different enlarged regions, respectively, e) the discrete distributions of two Raman peak intensities at micro-scale
and nano-scale mapping patterns, respectively.

8
C. Wang et al. Applied Surface Science 603 (2022) 154445

reveals that the excellent horizontal (x-y) SERS uniformity can be ach­ S11, Supporting Information). Clearly, the Raman signals can also be
ieved at almost all 2D planar surfaces of Au NPs@h-BN/BNCs. On the well repeated on the random planar points at different vertical depths,
other hand, we found that the poor Raman signal homogeneity with high supporting the receivable signal homogeneity along in-depth direction.
RSD value of 10.45% was recorded at different random points on the Moreover, based on the Raman peak intensity at 1617 cm− 1, the detailed
bare Au NPs@h-BN hybrids (Figure S10, Supporting Information). It is 3D Raman mapping diagrams at different depths (0 ~ 3.0 µm) are shown
mainly due to the “coffee ring” pattern of the dried droplet of colloidal in Fig. 8a. It reveals the excellent vertical Raman signal homogeneity,
analytes on hydrophobic substrates. So, the large-scale 2D spatial SERS which can be further confirmed by the variations of peak intensities
uniformity is related to the hydrophilic nature of the established Au versus different depths (Fig. 8b-e). Taken together, the obtained Au
NPs@h-BN/BNCs. NPs@h-BN/BNCs possess exceptional 3D spatial SERS uniformity at
Based on the established Au NPs@h-BN/BNCs, then the unique both horizontal (x-y) planar surface and vertical (z) in-depth direction.
vertical SERS uniformity along the in-depth direction was further The distinctive feature is dependent on the following two facts. The
illustrated here. The vertical Raman signals were recorded by changing essential condition is the homogeneous distribution of SERS hotspots via
the penetration of incident laser-focus-point to excite probe molecules monodisperse Au NPs firmly loaded on 2D h-BN, then the hybrids uni­
below the upper surface of 3D structures. The attainable maximum formly grafted into 3D BNCs. The predominant factor is the homoge­
depth is about 3.0 µm, which is determined by the thickness of nano­ neous distribution of colloidal analytes without any “coffee-ring”
products (Fig. 2e). Moreover, every experimental result at each vertical patterns among the 3D architecture. It is attributed to the ultra-rapid
depth was recorded by averaging the plane-scanning Raman signals and uniform-liquid diffusion of the injected droplets throughout the
performed on 100 × 100 µm2 areas. Then, the Raman tests of 10-11 M CV entire super-hydrophilic body. Therefore, the striking 3D spatial SERS
molecules were performed at different vertical depths of 0.5, 1.5, 2.5 uniformity is more suitable for reliable and repeatable analysis at
and 3.0 µm below the upper surface of the 3D SERS substrate (Figure random points over the whole Au NPs@h-BN/BNCs.

Fig. 8. a) Based on the established Au NPs@h-BN/BNCs, the 3D mapping diagrams of Raman peak intensity of 10-11 M CV molecules at 1617 cm− 1
along the vertical
(z) in-depth direction, b-e) the variations of Raman peak intensities versus the vertical depths.

9
C. Wang et al. Applied Surface Science 603 (2022) 154445

On the other hand, the effect of different molecular concentrations illustrated in Fig. 9e. The Raman signals derived from different batches
on the spatial SERS uniformity of Au NPs@h-BN/BNCs was also illus­ are very similar to each other, and the variations of Raman peak in­
trated here. In detail, two groups of CV molecules with high (10-6 M) tensities at 1617 and 1173 cm− 1 are then shown in Fig. 9f. The corre­
concentration and low (10-15 M) were then separately selected in this sponding RSD values are separately calculated about 0.89% and 2.73%,
section. Based on the Raman spectra of 10-6 M CV molecules at different confirming the excellent SERS reproducibility of the established Au
random 20 points (Figure S12a, Supporting Information), the mapping NPs@h-BN/BNCs. Besides, the time stability of SERS substrate was also
columns of characteristic bands and the variations of Raman peak in­ investigated in Figure S13 (Supporting Information). The Raman signals
tensities (1617 and 1173 cm− 1) are displayed in Fig. 9a-b. Based on the of CV molecules can be well maintained after keeping them for 30 days.
repeatable Raman signals, the RSD values of the above two Raman peaks The slight drops of characteristic peak intensities at 1617 cm− 1 with
are calculated about 1.38% and 2.15%, respectively. Thus, the excellent only ~ 3.5% lower than the initial ones can verify the good SERS sta­
homogeneous spatial distribution of Raman signals can be still verified bility of Au NPs@h-BN/BNCs. It is conceivable that the easy-to-
at high concentration of probe molecules. On the other hand, the reliable tailorable and reproducible SERS sensors are suitable for commercial
SERS uniformity of Au NPs@h-BN/BNCs would be also confirmed by the production toward practical applications.
Raman signals of probe molecules at low concentration, as shown in Taking full advantages of the above competitive SERS merits, the
Figure S12b (Supporting Information) and Fig. 9c-d. In detail, the cor­ obtained Au NPs@h-BN/BNCs were then practically applied to the ul­
responding RSD values in Fig. 9d are about 1.64% and 2.52%, respec­ trasensitive detections of toxic and carcinogenic polycyclic aromatic
tively. Therefore, the obtained Au NPs@h-BN/BNCs with remarkable hydrocarbons (PAHs). The PAHs with two or more benzene rings
SERS uniformity are extensively applied to the ultrasensitive monitoring generally originated from the incomplete combustion of coal, petro­
of probe molecules in a wide concentration range. Moreover, in order to leum, and other fossil fuels, resulting in serious hazardous effects on
further reveal the SERS reproducibility, the Raman spectra of 10-11 M CV ecological environment [52–54]. However, the intrinsic nonpolar nature
molecules performed on different 10 samples from different batches are of PAHs with less metal-affinity functional groups can’t enable them to

Fig. 9. Based on two groups of CV molecules

with high (10-6 M) and low (10-15 M) concentra­
tions, a-b) and c-d) the mapping columns of
characteristic bands at random 20 points and the
corresponding variations of Raman peak in­
tensities at 1617 and 1173 cm− 1 versus different
points on the Au NPs@h-BN/BNCs. e) The Raman
tests of 10-11 M CV molecules performed on
different 10 samples. f) The corresponding vari­
ations of Raman peak intensities at 1617 and
1173 cm− 1 versus different samples.

10
C. Wang et al. Applied Surface Science 603 (2022) 154445

be effectively detected in most cases of traditional SERS substrates better than many previous results based on dual-phase-accessible hot­
[52,55,56]. The routine efforts have been dedicated to functionalizing spot [59], supramolecular plasmonic films [58], Au NPs/hydrophobic
the nano-substrates via polymer organic molecules that would result in porous polymer [57], Ag/Cu fibers [60], Au NPs/molecularly imprinted
secondary pollution in SERS-based environmental surveillance. In this polymer (MIP) [61], etc. The enhanced detection is also highly related to
work, the super-hydrophilic Au NPs@h-BN/BNCs without any surface the unique super-hydrophilic SERS substrates that enable the colloidal
chemical modifications can directly give rise to the SERS sensitive de­ PAHs to be sharply diffused and completely penetrated into them. Then,
tections of anthracene and pyrene molecules that served as two repre­ the PAHs during the above rapid liquid-penetration process can be
sentative PAHs. The Raman spectra of anthracene molecules with significantly close to the Au NPs@h-BN hybrids that are grafted into 3D
different concentrations of 10-4 ~ 10-9 M are shown in Fig. 10a. The two opening-porous BNCs. The shortened distance between PAHs and SERS
prominent characteristic bands at 395 and 751 cm− 1 are attributed to active sites is beneficial for promoting the Raman signals. On the other
the skeletal deformation and stretching of benzene rings [57,58]. The hand, the experimental tests of PAHs were also performed on the bare
LOD of anthracene molecules can be achieved at low concentration of Au NPs@h-BN hybrids with poor wettability (Figure S14, Supporting
10-9 M (nanomole, nM) level. The well-defined linear relationships be­ Information). There is no obvious Raman signal that can be detected on
tween Raman peak intensities and molecular concentrations (Fig. 10b) the hydrophobic substrates, even at high concentrations of 10-4 M
facilitate the reliable SERS monitoring in practical scenarios. As for anthracene or 10-4 M pyrene molecules. It implies less SERS activity of
Raman spectra of pyrene molecules (Fig. 10c-d), the main characteristic traditional plasmonic NPs@semiconductors toward these specific probe
bands are detected at 406 and 594 cm− 1 that should be ascribed to the molecules. Therefore, the unique SERS advantage of super-hydrophilic
ring deformation and ring breathing [58]. The Raman signals of pyrene Au NPs@h-BN/BNCs in this work is highlighted by the ultralow detec­
molecules are also clearly distinguishable even the concentration as low tion of non-adsorptive PAHs. Moreover, the good linear fittings of
as 10-12 M in Fig. 10c. The resultant ultralow LOD of PAHs in this work Raman peak intensities at 406 and 594 cm− 1 versus molecular concen­
supports the excellent detectability of Au NPs@h-BN/BNCs. It is already trations are then plotted in Fig. 10d. Then, the SERS distinguishability of

Fig. 10. Based on the established Au NPs@h-BN/

BNCs, the ultrasensitive SERS detections of toxic
PAHs: a) Raman spectra of anthracene molecules
with concentrations of 10-4 ~ 10-9 M and b) the
variations of Raman peak intensities at 395 and
751 cm− 1 versus different molecular concentra­
tions, c) Raman spectra of pyrene molecules with
concentrations of 10-5 ~ 10-12 M and d) the var­
iations of Raman peak intensities at 406 and 594
cm− 1 versus different molecular concentrations.
e) the simultaneous SERS detection of 10-6 M
anthracene and 10-6 M pyrene in the mixed so­
lution. f) the practical SERS detection of pyrene
PAHs remained on children’s toys.

11
C. Wang et al. Applied Surface Science 603 (2022) 154445

the established Au NPs@h-BN/BNCs is also illustrated by simultaneous SERS substrate should be partly attributed to the formation of Schottky
detection of the mixed samples with anthracene and pyrene molecules barrier between plasmonic Au NPs and semiconductor h-BN nanosheets.
(Fig. 10e). The characteristic bands of two different PAHs can be clearly According to the previous literatures [63–66], the work function of Au
identified in the mixture condition, supporting the good spectral NPs dominated by (1 1 1) crystal plane is higher than that of h-BN
distinguishability. Furthermore, the tailorable and flexible SERS sub­ nanosheets, resulting in the generation of Schottky barrier on their in­
strates with easy-portability were also applied to the reliable detection terfaces. It can effectively improve the transfer of photo-excited elec­
of pyrene molecules absorbed on the children’s toys with rugged sur­ trons from the semiconductor to the plasmonic metal and then suppress
faces (Fig. 10f). The quantitative evaluation was conducted by analyzing the recombination of photo-generated electron-hole pairs, facilitating
the target recoveries via the standard addition method [62], via adding high-performance photocatalytic degradation [63,67,68]. In this way,
pyrene molecules with some known concentrations (10-5, 10-7, 10-9 and the repeated SERS tests of CV molecules would be effectively performed
10-11 M) on the irregular surfaces. Based on the variations of Raman on the same substrate (Fig. 11b-c). The experiments clearly reveal that
signal intensities, the recovery rates of pyrene molecules are calculated the Raman signals with ~ 93.7% peak intensities with respect to initial
~ 101.1%, 97.6%, 97.4% and 96.3% in Table S2 (Supporting Informa­ ones are maintained after five recycles, supporting the good SERS sta­
tion). These reliable experimental results confirm that the established bility of Au NPs@h-BN/BNCs. On the other hand, the photocatalytic
SERS sensor possesses a great potential for quantitative monitoring of degradation that is only performed at the near-surface of the SERS
toxic pollutants in real-world scenarios. substrate is not suitable for eliminating non-absorptive pyrene mole­
Finally, the Au NPs@h-BN/BNCs based SERS sensor in this work cules. Fortunately, the heating treatment of non-thermostable PAHs is
should also possess excellent reusability/recyclability under repeated expected to remove the analytes from the SERS substrate for recycling
tests, which is an important indicator for widespread applications. To tests, due to the intrinsic thermal stability of Au NPs@h-BN/BNCs. Based
verify this, two types of different analytes were selected here, including on the thermal treatment at 80 ℃ condition, the Raman spectra of
CV molecules with high accessibility to SERS substrate and non- pyrene molecules at different heating time (0 ~ 60 min) are shown in
adsorptive pyrene molecules with less substrate-affinity functional Fig. 11d. Apparently, the thermal-assisted elimination of pyrene mole­
groups. As for the thermostable dyes during the recyclable SERS tests, cules is effectively performed in this work, since the two Raman peak
the elimination of CV molecules after each measurement can be ach­ intensities steadily decrease during heating treatment. As shown in
ieved by photocatalytic degradation. The Raman spectra of CV mole­ Fig. 11d, the variation of Raman peak intensity at 406 cm− 1 confirms
cules via xenon lamp light-triggered photocatalytic degradation at that the most (99.8%) of pyrene molecules can be eliminated from the
different irradiation times are illustrated in Fig. 11a. It is shown that the SERS substrate after 60 min. Then, the five repeated tests performed on
Raman peak intensities of CV molecules progressively decrease with an the same SERS substrate are shown in Fig. 11e-f. About 96.7% Raman
increase in light irradiation time (0 ~ 90 min). For instance, the Raman peak intensities of pyrene molecules have been retained after five
peak intensity at 1617 cm− 1 drastically drops from about 29,030 a.u at repeated Raman tests, revealing the thermal-assisted SERS recyclability
initial condition to ~ 75 a.u after 90 min photocatalytic degradation. of Au NPs@h-BN/BNCs. Compared to many previous recyclable SERS
About 99.7% of CV molecules have been completely removed from the substrates with only one approach for removing analytes, the excellent
SERS substrate, ensuring that the same sample can be used for subse­ reusability of Au NPs@h-BN/BNCs can be realized by two different
quent Raman tests. The effective photocatalytic performance of the efficient strategies. The elimination of dyes with strong π-π interactions

Fig. 11. a) Based on the established Au NPs@h-BN/BNCs, the Raman spectra of 10-10 M CV molecules via photocatalytic degradation at different reaction times (0 ~
90 min), b) the recycling Raman spectra on the same sample, c) the variations of peak intensity at 1617 cm− 1 versus five repeated tests, d) the Raman spectra of 10-6
M pyrene molecules via thermal-assisted elimination at different heating time (0 ~ 60 min), e) the repeated Raman signals of pyrene molecules on the same sample, f)
the variations of peak intensity at 406 cm− 1 versus five recycling tests.

12
C. Wang et al. Applied Surface Science 603 (2022) 154445

between analytes and Au NPs@h-BN/BNCs can be achieved by the enhanced Raman spectroscopy characterization of native protein structures, Nat.
Commun. 12 (2021) 1292.
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