3.
Results and discussion
SEM analyses were first conducted to obtain the
morphological information of the Rh-RhO x/PCN
sample. As shown in Fig. S1, a 2D graphene-like
morphology of the Rh-RhOx/PCN sample was clearly
observed. Meanwhile, we found that the edges of Rh-
RhOx/PCN sample rolled up due to surface tension,
which is similar to the general behavior of graphene.
These results obvious implied that the Rh-RhO x/PCN
sample still maintain the morphology of PCN
nanosheets. In addition, TEM analyses were performed
to obtain the more morphological information of the Rh-
RhOx/PCN sample. The TEM images of Rh-RhO x/PCN
show that the Rh-based cocata-lysts are distributed
separately on PCN nanosheets (Fig. 1a and Fig. S2). In
the HRTEM images (Fig. 1b), the nanoparticulate cocat-
alysts with average size of about 2–10 nm are observed
clearly. The distinct lattice fringes with an interplanar
spacing of 0.226 nm cor-respond to the (1 1 1) crystal
planes of metallic Rh, which suggests the formation of
Rh nanoparticles. The HRTEM image also indicates that
the RhOx species are nearly amorphous, perhaps because
they are generated at room temperature with low
crystallinity. The dis-tribution of Rh and RhO x
cocatalysts on PCN were examined by ele-mental
mapping tests. As shown in Figs. 2 and S3, the STEM
images give numerous bright specks, representing the
Rh-based nanopar-ticles. And the corresponding
elemental mapping images (Figs. 2, S3 and Table S1)
further demonstrate that the Rh and RhO x cocat-alysts
were load on the PCN surface with high dispersion and
rel-atively uniform distribution.
To reaffirm that Rh and RhOx nanoparticles are
successfully deposited on PCN, XPS tests were
performed. As presented in Fig. 3b, the Rh 3d XPS
spectrum can be well divided into four peaks positioned
at 307.8, 311.8, 309.5 and 314.1 eV, respectively. The
former two peaks correspond to the characteristic peaks
of metallic Rh [45], while the latter two peaks are
attributed to the Rh-O bonds [29]. This result was
further demonstrated by analyzing the Rh 3d XPS
spectrum of Rh/PCN and RhOx/PCN (Fig. S4). The
results of TEM and XPS characterizations indicate that
Rh and RhOx nanoparticles are loaded on PCN
nanosheets through the in situ photodeposition method
without using sacrificial agents. Compar-ison of the
binding energies of C 1s (Fig. S5a) and N 1s (Fig. S5c)
of Rh-RhOx/PCN with those of pure PCN nanosheets
(Fig. S5b and 5d) finds no noticeable changes, meaning
that depositing the cocata-lysts on PCN has no obvious
influences on its surface property [46,47].
To further study the influence of Rh and RhO x
cocatalysts on the PCN structure, texture and
composition, a series of physicochemi-cal
characterizations were performed. Firstly, the crystalline
struc-ture of as-synthesized sample was probed using
powder XRD. As shown in Fig. 4a, the PCN sample
shows two characteristic peak at 13.0 and 27.5L, which
could be attributed to the (1 0 0) and (0 0 2) crystal
planes of PCN, respectively [38,48]. It is well estab-
lished that the peak (1 0 0) derives from the in-plane
structural repeating units of tri-s-triazine, while the peak
(0 0 2) is assigned to the interlamellar reflection of a
graphitic-like structure. The XRD patterns of Rh-
RhOx/PCN were similar to that of pure PCN nanosheets,
suggesting that depositing the Rh and RhO x cocata-lysts
on PCN have no obvious influences on its crystal phase
struc-ture and crystallinity. The chemical structure of
PCN and Rh-RhOx/ PCN samples were further analyzed
by FTIR measurements. As shown in Fig. 4b, both pure PCN and Rh-RhOx/PCN samples shown

Fig. 1. Representative TEM (a) and HRTEM (b) images of Rh-RhO x/PCN sample

Fig. 2. STEM image and EDX elemental mapping of C, N, Rh and O for Rh-RhO x/PCN sample.
132 Z. Pan et al. / Journal of Catalysis 379 (2019) 129–137

Fig. 3. XPS characterization of Rh 3d for PCN (a) and Rh-RhO x/PCN (b) sample.

similar FTIR absorption peaks, suggesting loading Rh
and RhOx cocatalysts on PCN nanosheets don’t change
the core structure of the PCN framework. A sharp peak
could be observed at 812 cm 1, and it was assigned to the
characteristic heptazine bending mode. The strong
absorption band at 1200–1600 cm 1 are ascribed to the
characteristic stretching vibration modes of tri-s-triazine
rings, and the broad peak located at 3000–3600 cm 1 is
due to the absorbed H2O molecules and the stretching
vibration of terminal ANH groups of PCN [49,50]. In
addition, we carried out N2 adsorption-desorption
isotherms to study the influence of Rh and RhO x cocat-
alysts on the surface area of PCN. The BET surface area
(Fig. 4c) is ca. 65 m2 g 1 for PCN and 64 m2 g 1 for Rh-
RhOx/PCN. The pore
size distributions of PCN and Rh-RhOx/PCN samples
were tested by the BJH method. The result (Fig. S6)
shows that the pore sizes of Rh-RhOx/PCN sample were
similar to that of pure PCN nanosheets. All in all, these
results strongly imply that the modifi-cation of Rh and
RhOx species do not change the structure and chemical
skeleton of the PCN semiconductor [20].
The optical properties of the as-prepared materials
were inves-tigated by UV–Vis DRS. As shown in Fig.
4d, when the Rh and RhOx cocatalysts were introduced
into PCN nanosheets, the optical absorption properties
were obvious enhanced. This is mainly because the Rh
and RhOx cocatalysts have excellent absorption
properties in visible region. In addition, the specific
charge carrier
 Z. Pan et al. / Journal of Catalysis 379 (2019) 129–137
Fig. 4. (a) XRD patterns, (b) FTIR spectrum, (c) N 2 adsorption-desorption isotherm and (d) Uv–vis diffuse
reflectance spectra of PCN and Rh-RhOx/PCN samples.
dynamics of the Rh-RhOx/PCN photocatalyst are probed
by photo-luminescence (PL) analysis. As shown in Fig.
5a, the pure PCN nanosheets present a strong PL
emission peak at 460 nm, signifying the high
recombination rate of charge carriers. In comparison, PL
emission of Rh-RhOx/PCN reduces obviously, which
indicates that introducing Rh and RhO x cocatalysts on
PCN efficiently promote the separation of photoinduced
charges [47,51]. Meanwhile, the time resolved PL decay
profiles show that the average lifetime of Rh-RhO x/PCN
is 3.6 ns (Fig. 5b), much shorter than that of pristine
PCN nanosheets (e.g., 4.31 ns). The observed PL
quenching and life-time reduction indicate the quick
separation and migration of pho-togenerated electrons
and holes to the Rh and RhO x species, respectively,
which results in efficient separation of the charge car-
riers [3]. Fig. 5c shows the transient photocurrent
spectra of the materials. As can been seen, Rh-
RhOx/PCN delivers markedly enhanced current density
than pure PCN, reflecting the cocatalyst-modified PCN
nanosheets enable the accelerated trans-portation of
charges. Beasides, The typical cyclic voltammograms of
water reduction and water oxidation are shown in Fig.
S7. The significant decrease of overpotential clearly
reveals that the high activity for electrochemical water
splitting reaction could be attributed to the presence of
Rh and RhOx. This result indicates that Rh and RhOx can
efficiently promote water splitting electrocatalyt-ically.
In addition, the electrochemical impedance spectra (EIS)
dis-play that the Rh-RhOx/PCN electrode in the dark
gives a smaller
133
semicircle in the Nyquist plots (Fig. 5d), implying that
the elec-trode affords more efficient interface charge
transfer between the photocatalyst and electrolyte. On
the basis of these PL and electro-chemical tests, it is
concluded that the Rh and RhOx cocatalysts can
remarkably promote the transportation and suppress the
recombi-nation of photoinduced charge carriers.
To demonstrate the cocatalytic functions of Rh and
RhOx for water photosplitting, the HER and OER half-
reactions were first carried out. First, to investigate
whether Rh and RhOx nanoparticles could be used as the
reductive cocatalysts, photocatalytic H2 evo-lution
activities of PCN, Rh/PCN and RhOx/PCN samples were
tested in methanol aqueous solution under visible light
irradiation (k > 400 nm). As illustrated in Fig. 6a, the
pure PCN nanosheets are almost inactive for HER, and
RhOx/PCN shows a slightly improved activity for the
HER reaction. Of note, the Rh/PCN sample presents a
significantly enhanced HER efficiency. Such observa-
tions indicate that Rh is a highly active reductive
cocatalyst for HER. On the other hand, the OER half-
reaction performance of the samples was also measured
with AgNO3 as electron sacrificing agent under full arc
irradiation (k > 300 nm). The Rh/PCN sample manifest
a moderate O2-evoluting rate of 6.7 lmol h 1 (Fig. 6b),
which is very close to that of bare PCN nanosheets (6.4
lmol h 1), indicating that the Rh cocatalyst has no
obvious promotional effect to OER. However, the O2
production rate of RhOx/PCN is more than three times
higher than that of PCN, mainly because that the RhO x
134 Z. Pan et al. / Journal of Catalysis 379 (2019) 129–137

Fig. 5. (a) PL spectra and (b) time-resolved transient fluorescence decay of PCN and Rh-RhO x/PCN sample.
Transient photocurrents (c) and electrochemical impedance spectroscopy (d) of PCN and Rh-RhOx/PCN sample at
0.2 V vs SCE in 0.2 M Na2SO4 solution.

Fig. 6. Evolution of H2 (a) and O2 (b) from PCN, Rh/PCN and RhOx/PCN half reaction.

species can decrease the overpotential of OER [29].
These activity evaluations results prove that the Rh and
RhOx nanoparticles are highly active HER and OER
cocatalysts, respectively.
Next, photocatalytic overall water splitting performance
of the RhOx/PCN, Rh/PCN and
RhOx/PCN samples was evaluated. As shown in Fig. 7a,
the overall water photosplitting activity of Rh-
RhOx/PCN is obviously higher than those of RhO x/PCN
and Rh/
 Z. Pan et al. / Journal of Catalysis 379 (2019) 129–137 135

PCN. This is a strong indication that the co-deposition

of the Rh and RhOx cocatalysts can synergistically
promote photocatalytic overall water splitting efficiency
of PCN nanosheets. The AQY for the overall water
splitting reaction was calculated to be 0.1% at 420 nm.
Furthermore, the control experiments display that photo-
catalytic overall water splitting for H 2 and O2 evolution
presents a volcanic eruption plot when varying loaded
amounts of the Rh and PCN with visible light (k > 400
nm)RhOx nanoparticles (Fig. 7b). The 2%-Rh-
RhOx/PCN photocatalyst shows an optimal H 2 evolution
rate of 1.4 lmol h 1, accompanied by the almost
stoichiometric generation of O2 (i.e., 0.6 lmol h 1). On
further increase of the depositing content to 4%, the
photocat-alytic overall water splitting performance is
obvious reduced, sug-gesting that the excessive
depositing of Rh and RhOx cocatalysts might acts as
recombination center of photogenerated carriers and
impedes the optical absorption of PCN.

Fig. 7. (a) Water splitting rate of Rh/PCN, RhOx/PCN

and Rh-RhOx/PCN under full arc (k > 300 nm).
(b) Water splitting rate of different amounts of
Rh-based species deposited
PCN nanosheets under visible light (k > 400 nm).
(c) Wavelength dependence of overall water
splitting rate for Rh-RhOx/PCN sample. (d) Overall
water splitting by Rh-RhOx
 To further evaluate the photocatalytic performance of Rh-RhO x/ PCN, the overall water splitting reactions were
tested under differ-ent light irradiations controlled by using carious long-pass cutoff optical filters (Fig. 7c). The
activity of Rh-RhOx/PCN decrease with the increase in wavelength, and the variation trend of H 2/O2 pro-duction
matches well with its absorption spectrum. Such an obser-vation illustrates that the photocatalytic overall water
splitting process is mainly driven by light harvesting of the Rh-RhO x/PCN photocatalyst.
Stability of the Rh-RhOx/PCN photocatalyst was assessed by performing the reaction for consecutive five runs
(Fig. 7d). The photocatalytic overall water activity first increases and then decreases. Firstly, the inferior water
splitting rate in the first run compared to that in the second cycle, because the surface of fresh PCN sample contains
some unstable N-containing groups that will consume part of the photogenerated electrons and holes. Corre-
spondingly, the detected N2 formation rate in the first run (e.g., 6.7 lmol/4h) is obviously higher that the rate in the
second cycle (e.g., 2.1 lmol/4h). In addition, to explore the reasons for the activ-ity loss of Rh-RhO x/PCN, a series of
physicochemical characterizations were performed for the used sample. Results of FTIR and XRD analyses reveal
that the core chemical skeleton of Rh-RhO x/ PCN has no perceptible alternations after five catalytic cycles (Figs. S8
and S9), highlighting the high robustness of the PCN pho-tocatalyst in the reaction system. The SEM images (Fig.
S10) reveal that the morphology of Rh-RhO x/PCN had not obvious change after five catalytic cycles, further
suggesting the high stability of the PCN photocatalyst in the reaction system. However, the DRS spectra show that
the optical harvesting property of Rh-RhO x/PCN in the visible region is slightly strengthened after the photocatalytic
reac-tions (Fig. S11), which may be induced by the changes in particles sizes of the cocatalysts. To check the
structural variations of the cocatalysts after photocatalysis, TEM tests were conducted (Fig. S12). It is observed that
the size of the cocatalyst nanoparti-cles in the used Rh-RhO x/PCN sample increases significantly com-pared to that of
the fresh sample. These findings suggest that the photocatalytic activity of Rh-RhO x/PCN is closely related to the
cocatalysts size. Therefore, we believe that overall water splitting activity of Rh-RhO x/PCN could be further
improved by appropriate strategies to control the particles size of Rh-based cocatalysts, for example, by designing
core-shell-type cocatalysts [14,34,52].

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