A new Ni-diaminoglyoxime-g-C3N4complex towards efficient photocatalytic ethanol splitting: Via a ligand-to-metal charge transfer (LMCT) mechanism

Article abstract of DOI:10.1039/d0cc01120g

We report a novel Ni-diaminoglyoxime-g-C3N4 (Ni-DAG-CN) complex for H2 evolution through photocatalytic ethanol splitting. Compared to that of pristine g-C3N4, Ni-DAG-CN exhibits a 21-fold enhancement of photocatalytic activity (296.1 μmol h-1 g-1) under irradiation with excellent stability. The enhanced photocatalytic activity can be attributed to a proposed ligand-to-metal charge transfer (LMCT) mechanism, which is illustrated both experimentally and theoretically. This work provides great potential in the future design of low-cost, high-performance photocatalysts for H2 evolution from alcohol splitting.

Full text of DOI:10.1039/d0cc01120g

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A new Ni-diaminoglyoxime-g-C N complex towards efficient
3
4
photocatalytic ethanol splitting via ligand-to-metal charge transfer
LMCT) mechanism
(
Received 00th January 20xx,
Accepted 00th January 20xx
Yanqi Xu, Cui Du, Chen Zhou and Shengyang Yang a*
a
a
b*
DOI: 10.1039/x0xx00000x
We report a novel Ni-diaminoglyoxime-g-C
complex for photocatalytic H evolution through ethanol
splitting. Compare to that of pristine g-C , Ni-DAG-CN
exhibits a 21-fold enhancement on photocatalytic activity
3 4
N (Ni-DAG-CN)
2
3 4
N
-1
-1
(296.1 mol h
g ) under irradiation with excellent
stability. The enhanced photocatalytic activity can be
attributed to a proposed ligand-to-metal charge transfer
(
LMCT) mechanism, which is illustrated both experimentally
and theoretically. This work provides great potentials to the
future design of low-cost, high-performance photocatalysts
for alcohol splitting H
2
evolution.
Hydrogen (H ) is emerging as clean energy to address the
2
Scheme 1 Schematic illustration of the synthesis of Ni-DAG-CN
complex.
urgent energy demand and associated environmental
pollution by conventional fossil fuel.1 While the
2
transportation and storage of H remain a great challenge
due to its physical properties, recent studies revealed
promising approaches to tackle this issue by utilizing
transfer (MLCT) mechanism draws more consideration
because the internal low energy electron pathway created
through MLCT can significantly expand its photocatalytic
potential. Nevertheless, limitations on cost and catalytic
performance still severely hinder its application on
2
small molecular alcohols from biomass fermentation as
8
3
H
2
storage media. One main route is to produce H
2
through ethanol reforming, which, however, requires
photocatalysis.
high temperature and pressure, and often includes side
In this work, we propose a ligand-to-metal charge transfer
2 4
reactions with carbonic by-products (CO , CH
and etc.).3
a,
(
LMCT) mechanism with a novel Ni-diaminoglyoxime-g-C
complex(denoted as Ni-DAG-CN) for enhanced photocatalytic
evolution from ethanol splitting. Compare to that of
pristine g-C the Ni-DAG-CN exhibits 21-fold
3 4
N
4
In this context, alternative explorations on ethanol
dehydrogenation to aldehyde via photocatalysis began to
attract significant attention due to its high selectivity,
H
2
3
N
4
,
a
mild reaction conditions, and most importantly, the
-1
-1
utilization of inexhaustible solar energy.5
enhancement on photocatalytic activity (296.1 mol h g )
with excellent photostability. The direct splitting of ethanol
into H and aldehyde at room temperature with no CO
2 x
Graphitic carbon nitride (g-C
and toxic-free photocatalyst that has been demonstrated
evolution.6 To enhance its
for photocatalytic H
3 4
N ) is a low-cost, stable
formation is highly desired for future green energy
2
9
advancement.
photocatalytic activity, different strategies including
heteroatom doping, microstructure modification, and co-
The design of the novel Ni-DAG-CN complex was displayed
in Scheme 1 and the synthesis details were summarized in ESI.
7
catalyst coupling have been explored. Recently, a unique
1
H NMR and FT-IR spectra confirmed the successful
engineering concept through the metal-to-ligand charge
1
0
fabrication of DAG (Fig. S1). Diffraction peaks at 13.1° and
7.1° in XRD patterns of g-C and 1 wt% Ni-DAG-CN can be
attributed to (100) and (002) crystal planes of graphitic
2
3 4
N
a.School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou
2
25002, P.R. China. E-mail: syyang@yzu.edu.cn
1
1
b.
materials (JCPDS-87-1526), respectively (Fig. S2). Notably,
the diffraction peaks of Ni and NiO were not presented in the
XRD patterns (Fig. S2), suggesting no Ni and NiO species in the
School of Natural Sciences, University of Central Missouri, Warrensburg, Missouri
6
4093, USA. E-mail: zhou@ucmo.edu
x
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
x
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Journal Name
synthesized Ni-DAG-CN complex. TEM and EDX were binding energy (Fig. 1b, c). These energy shifts not only
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DOI: 10.1039/D0CC01120G
employed to further verify the state of Ni. The results showed indicated strong interactions among Ni, DAG and CN
no lattice spacing of Ni or NiO
(
x
nanoparticles in TEM images through complexation, but also suggested a higher
Fig. S3a-c), while the corresponding EDX image revealed the electron concentration environment in 1 wt% Ni-DAG-CN
1
7
existence of Ni element (Fig. S3d). The elemental mapping according to “electron screening effect”. As a result, the
images demonstrate C, N, Ni, and O elements were uniformly promotion of charge separation from g-C to Ni(II)
distributed (Fig. S4). In addition, the interaction between the could improve the photocatalytic activity of Ni-DAG-CN.
3 4
N
Ni and DAG-CN was revealed by the FT-IR spectra (Fig. S5).
Negative shifts were observed from the representative tri-s-
The Ni-DAG-CN displayed significantly enhanced
photocatalytic H evolution from ethanol. The highest
hydrogen evolution rate of 296.1 mol h g , which is 21
2
-1
-1
-1
-1
triazine peaks at 809 cm and between 1100 and 1700 cm ,
indicating the coordination bonds formation between the Ni(II)
times higher than that of pristine g-C
from 1 wt% Ni-DAG-CN (Fig. 1d). Further increment of Ni
wt% in Ni-DAG-CN resulted in decrease in H evolution
rate, which can be explained by the light shield effect
3 4
N , was observed
1
2
and DAG-CN. The successful incorporation of DAG and Ni in
the as-prepared 1 wt% Ni-DAG-CN also resulted in slightly
2
1
3
3 4
decreased surface area compared to that of g-C N (Fig. S6).
1
8
caused by the amount of Ni. Additionally, H
performances of 1 wt% Ni/CN and 1 wt% NiO
both tested for comparison (Figure S8). The 1 wt% Ni-
DAG-CN exhibited much higher H -evolution rate than
those of 1 wt% Ni/CN and 1 wt% NiO /CN. Time-
dependent H production test showed almost a linear
2
-evolution
To provide insights on the electronic states of Ni-DAG-
CN complex, X-ray photoelectron spectroscopy (XPS) was
employed. The survey spectrum of 1 wt% Ni-DAG-CN
confirmed the existence of C, N, Ni and O elements (Fig.
S7a). Two strong peaks of Ni 2p3/2, Ni 2p1/2 at 856.4 eV and
x
/CN were
2
x
8
73.9 eV and their corresponding satellite peaks
confirmed the Ni(II) state in the 1 wt% Ni-DAG-CN
2
increase in 6 h period (Fig. 1e), and no obvious decline was
observed from the 18 h cyclic test (Fig. 1f), suggesting
excellent photocatalytic stability of Ni-DAG-CN complex.
1
4
0
sample. The absence of Ni signals from XPS further
indicated the lack of Ni particles in the Ni-DAG-CN. In
the O 1s spectrum of 1 wt% Ni-DAG-CN, two peaks at
1
5
x
No CO was generated during photocatalysis based on the
monitor from an online gas chromatography flame
ionization detector (GC-FID) system (Fig. S9a-c). In
addition, acetaldehyde was also produced and its
concentration in the solution after photocatalysis was
determined to be up to 0.082 mg/L (Fig. S9d). Besides
fatty alcohol (ethanol), the Ni-DAG-CN complex can be
also employed to photocatalytic aromatic alcohol
oxidation. Surprisingly, the optimum conversion and
selectivity of benzyl alcohol for 1 wt% Ni-DAG-CN reached
5
32.8 eV and 531.6 eV shifted to lower binding energy
and a new peak appeared at 530.7 eV, implying a g-C
structural change after the introduction of DAG and Ni(II)
Fig. S7b). Similarly, no binding energy peaks that can be
attributed to NiO were observed in Ni-DAG-CN
complex. In addition, compared to the 288.5 eV found
from C 1s spectrum of g-C , lower binding energy of C
S at 288.2 eV was shown in 1 wt% Ni-DAG-CN. The N 1s
3 4
N
(
x
1
6
3 4
N
1
peaks of 1 wt% Ni- DAG-CN were also shifted to lower
7
4.1% and 99% when irradiated for 24 h, respectively
(Table S3). These results suggested that the complexation
of Ni and DAG into CN was fundamentally beneficial to
alcohol splitting photocatalytic activity and stability.
This significantly enhanced photocatalytic activity from
Ni-DAG-CN was further investigated with diverse
spectroscopic characterizations for fundamental
understandings. Light absorption is a vital factor for
photocatalytic reactions. Compared with pristine g-C
the increased light absorption of Ni-DAG-CN can
contribute to higher photocatalytic H evolution activity
Fig. S10a). The bandgaps of g-C and 1 wt% Ni-DAG-CN
3 4
N ,
2
(
3 4
N
were estimated to be 2.79 and 2.75 eV, respectively (Fig.
S10b). A significantly decreased slope of Mott-Schottky
plots further indicated a contribution to photocatalytic
activity enhancement through increased donor densities
1
9
(Fig. 2a). The band structures of CN and 1 wt% Ni-DAG-
CN were illustrated based on the Mott- Schottky plots
and valence band (VB)-XPS spectra (Fig. 2b-d), which
were consistent with the UV-vis results. Charge
separation efficiency is also crucial to photocatalysis
apart from light absorption and band structure. Compare
Fig. 1 XPS spectra of CN and 1 wt% Ni-DAG-CN complex: (a) Ni 2p (b)
2
C 1s, (c) N 1s, and (d) photocatalytic H evolution rates of CN and Ni-
DAG-CN irradiated by a 300 W Xenon-lamp (λ > 350 nm), (e) H
production over 6 h for CN and 1 wt% Ni-DAG-CN (λ > 350 nm), (f)
Cyclic H production of 1 wt% Ni-DAG-CN complex.
2
3 4
to that of pristine g-C N , 1 wt% Ni-DAG-CN displayed a
2
2
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC01120G
Fig. 4 Diagram of photocatalytic mechanism for enhanced ethanol
splitting according to theoretical calculations and (b) proposed
reaction process in details.
and 1.86 eV, respectively. This result confirmed the
indispensable role of introduced DAG and Ni(II) for
narrowed bandgaps. Moreover, electrostatic potential
Fig. 2 (a) Mott-Schottky plots of CN and 1 wt% Ni-DAG-CN at
1
3
000 Hz. (b) Mott-Schottky plots of 1 wt% Ni-DAG-CN at 1000,
000 and 5000 Hz. (c) VB-XPS of CN and 1 wt% Ni-DAG-CN. (d)
(
ESP) map of Ni-DAG-CN model (Figure S12) was applied
to analyze charges of the elements. According to the ESP
map result, electron density of metal (Ni) was
Band energy position of CN and 1 wt% Ni-DAG-CN.
lower fluorescence intensity in the photoluminescence considerably higher than that of C
PL) spectra. This observation suggested improved suggested the electron transfer from CN to Ni(II) via LMCT
efficiencies of charge separation from 1 wt% Ni-DAG-CN mechanism. Based on the above analysis, a feasible LMCT
3 4
N . This result
(
2
0
(
Fig. S11a). In addition, the enhanced charge separation mechanism is proposed in Fig. 4. The reduced bandgap
of 1 wt% Ni-DAG-CN can be also verified from time- and the lower theoretical LUMO of Ni-DAG-CN than that
resolved fluorescence (TRFL), in which a longer lifetime of of C are ideal for photocatalytic ethanol splitting for H
fluorescence decay was observed (Fig. S11b). Moreover, evolution. Specifically, the Ni-DAG-CN complex can be
and Ni-
N
3 4
2
2
1
3 4
the smaller radius of Nyquist plot from electrochemical treated as a heterojunction composed of g-C N
-
impedance spectroscopy (EIS) tests (Fig. S11c) and larger DAG-CN units. Under light irradiation, electrons (e ) and
+
photocurrent response (Fig. S11d) both also implied that holes (h ) were generated on the conduction band (CB)
-
1
wt% Ni-DAG-CN possessed better separation of charge and valence band (VB) of CN. Afterward, e on CB of g-
2
2
carriers compared to that of g-C
3
N
4
.
C
3
N
4
transferred onto CB of Ni-DAG-CN via LMCT
evolution from ethanol
3 4
N
to Ni(II) could enhance the splitting (Fig. 4a). A possible reaction process was
The above results strongly support that the charge mechanism for enhanced H
2
transfer from g-C
+
photocatalytic activity of Ni-DAG-CN complex. Therefore, illustrated in Fig. 4b. Firstly, h on VB activated ethanol,
+
23
simulations at the density functional theory (DFT) level forming ethoxy species (•CH
were carried out to propose the fundamental mechanism •CH CH OH then interacted with Ni-DAG-CN to provide
CH O-Ni-DAG-CN. Afterwards, the formed
O-Ni-DAG-CN further interacted with Ni-DAG-CN
2 2
CH OH) and proton (H ).
2
2
(
Fig. 3). As illustrated in this calculation, the charge on the metastable CH
2
2
highest occupied molecular orbital (HOMO) of 1 wt% Ni- CH
2
CH
2
3 4
DAG-CN was mainly distributed on g-C N
, while the to generate a metastable intermediate which then
charge distribution on its lowest unoccupied molecular dissociated to acetaldehyde and H-Ni-DAG-CN.24
-
orbital (LUMO) was concentrated on Ni(II). Previous Meanwhile, e on CB can easily transfer to the Ni(II) via
studies have demonstrated that the incorporation of the LMCT mechanism, which further reacted with H-Ni-
+
25
2
Cu(II) and 1,2,4,5-benzenetetracarboxylic acid (BTEC) DAG-CN and H to produce H .
could lead to narrower bandgaps;19 similarly, Ni(II) and
The free energy profiles for the overall reactions were
DAG also played an essential role in reduced bandgaps of calculated to provide further evidence for on the
Ni-DAG-CN. As shown in Table S4, the calculated proposed process (Fig. 5). Step M1 to M2 was an
theoretical bandgaps of g-C
N
3 4
and Ni-DAG-CN were 2.70 endothermic process. Photons can provide energy to
allow this photocatalytic reaction, promoting the
interaction between •CH
2 2
CH OH and Ni-DAG-CN to form
metastable CH CH O-Ni-DAG-CN. Step M3 to M4 was an
2
2
exothermic reaction, which provide the reasonability for
the further interactions between Ni-DAG-CN and
CH CH O-Ni-DAG-CN. Afterwards, the metastable
2 2
intermediate generated in the previous step reacted with
H• to form acetaldehyde and H-Ni-DAG-CN in the step
+
M5 and M6. Finally, the reaction among H-Ni-DAG-CN, H
and e transferred via the LMCT mechanism could easily
Fig. 3 Diagram of charge excitation pathway in the unit model of Ni-
DAG-CN.
-
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was synthesized and displayed a 21-time enhancement of
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theoretical calculations. This work provides great potential
to the future design of low-cost, high-performance
1
1
2
photocatalysts for alcohol splitting H evolution.
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Table of Content (TOC)
A Ni-diaminoglyoxime-g-C N complex is developed for photocatalytic ethanol
3
4
splitting H evolution via a ligand-to-metal charge transfer mechanism.
2