Carbon Nitride Supported High-Loading Fe Single-Atom Catalyst for Activation of Peroxymonosulfate to Generate 1O2 with 100 % Selectivity

Article abstract of DOI:10.1002/anie.202109488

Singlet oxygen (¹O₂) is an excellent active species for the selective degradation of organic pollutions. However, it is difficult to achieve high efficiency and selectivity for the generation of ¹O₂. In this work, we develop a graphitic carbon nitride supported Fe single-atoms catalyst (Fe₁/CN) containing highly uniform Fe-N₄ active sites with a high Fe loading of 11.2 wt %. The Fe₁/CN achieves generation of 100 % ¹O₂ by activating peroxymonosulfate (PMS), which shows an ultrahigh p-chlorophenol degradation efficiency. Density functional theory calculations results demonstrate that in contrast to Co and Ni single-atom sites, the Fe-N₄ sites in Fe₁/CN adsorb the terminal O of PMS, which can facilitate the oxidization of PMS to form SO₅^.?, and thereafter efficiently generate ¹O₂ with 100 % selectivity. In addition, the Fe₁/CN exhibits strong resistance to inorganic ions, natural organic matter, and pH value during the degradation of organic pollutants in the presence of PMS. This work develops a novel catalyst for the 100 % selective production of ¹O₂ for highly selective and efficient degradation of pollutants.

Full text of DOI:10.1002/anie.202109488

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Accepted Article
Title: Carbon Nitride Supported High-Loading Fe Single-Atom Catalyst
for Activating of Peroxymonosulfate to Generate 1O2 with 100%
Selectivity
Authors: Longshuai Zhang, Xunheng Jiang, Ziai Zhong, Lei Tian, Qing
Sun, Yitao Cui, Xin Lu, Jian-Ping Zou, and Shenglian Luo
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202109488
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10.1002/anie.202109488
Angewandte Chemie International Edition
COMMUNICATION
Carbon Nitride Supported High-Loading Fe Single-Atom Catalyst
for Activating of Peroxymonosulfate to Generate 1O2 with 100%
Selectivity
Long-Shuai Zhang,†[a] Xun-Heng Jiang,†[a] Zi-Ai Zhong,[a] Lei Tian,[a] Qing Sun,[a] Yi-Tao Cui,[b] Xin Lu,[c]
Jian-Ping Zou*[a] and Sheng-Lian Luo[a]
[a]
Dr. L. S. Zhang, Dr. X. H. Jiang, Z. A. Zhong, L. Tian, Q. Sun, Prof. J. P. Zou, Prof. S. L. Luo
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle
Nanchang Hangkong University
Nanchang, Jiangxi 330063, P. R. China
E-mail: zjp_112@126.com.
[b]
[c]
Prof. Y. T. Cui
SANKA High Technology Co. Ltd. 90-1
Kurimachi, Shingu-machi, Tatsuno, Hyogo 679-5155, Japan
Prof. X. Lu
State Key Laboratory of Physical Chemistry of Solid Surface
Xiamen University
Xiamen, Fujian 361005, P. R. China
[†]
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of the document.
Abstract: Singlet oxygen (1O2) is an excellent active species for the
selective degradation of organic pollutions. However, it is difficult to
achieve high efficiency and selectivity for the generation of 1O2. In
this work, we develop a graphitic carbon nitride supported Fe single-
atoms catalyst (Fe1/CN) containing highly uniform Fe-N4 active sites
with a high Fe loading of 11.2 wt%. The Fe1/CN achieves generation
of 100% 1O2 by activating peroxymonosulfate (PMS), which shows
an ultrahigh p-chlorophenol degradation efficiency. Density
functional theory calculations results demonstrate that in contrast to
Co and Ni single-atom sites, the Fe-N4 sites in Fe1/CN adsorb the
Therefore, there is an urgent need to develop new catalysts for
highly selective and efficient generation of 1O2.
Single-atom catalysts (SACs), which showed higher selectivity
and efficiency in catalytic reactions than those of traditional
catalysts, have been used to activate PMS for the generate of
1O2.[9] And N-doped carbon supported SACs have exhibited
significantly enhanced 1O2 generation selectivity from the
activated PMS. However, the mechanism of enhancement by
different SACs vary, indicating that the metal atoms affects the
selectivity of 1O2.[10] Recently, theoretically constructed CoN2+2
SACs achieved a selectivity higher than 98% for the generation
of 1O2 by activating PMS, which proved that the coordination
atoms also play an important role in the selective generation of
1O2.[11] The various types of N atoms present in the supports of
SACs alter the different adsorption and activation mechanisms
terminal O of PMS, which can facilitate the oxidization of PMS to
•-
form SO5
,
and thereafter efficiently generate 1O2 with 100%
selectivity. In addition, the Fe1/CN exhibits strong resistance to
inorganic ions, natural organic matter, and pH value during the
degradation of organic pollutants in the presence of PMS. This work
develops a novel catalyst for the 100% selective production of 1O2
for highly selective and efficient degradation of pollutants.
•
of PMS. Consequently, the generation of OH, SO4•-, and other
radicals have not been eliminated to date.[12] Furthermore, the
sparse doping of N, which fixes the metal atoms by coordination,
causes the low metal loading, which retards the generation of
1O2.[13] Therefore, the SACs having uniformly structured supports
and abundant active sites are required for the selective
Singlet oxygen (1O2) is
a weak oxidant that has strong
electrophilicity and selectivity removes electrons from electron-
rich substances.[1] Therefore, it is commonly used in the fields of
green organic synthesis, photodynamic cancer treatment, and
sewage purification.[2] Due to its long life, wide pH tolerance, and
high selectivity, 1O2 exhibits stronger resistance to
environmental interference and higher selectivity of degradation
than hydroxyl radicals (•OH) and sulfate radicals (SO4•-),
particularly in the field of wastewater treatment.[3] Currently, the
disproportionation of superoxide radical (O2•-), which is produced
1
generation of O2. Graphitic carbon nitride (CN) has specified C
and N sites and high N content, resulting in abundant and
uniform single atomic fixation sites.[14] Consequently, when CN is
used as the support, the obtained SACs would exhibit highly
uniform and densely loaded metal active sites that facilitate the
highly efficient activation of PMS to generate 1O2 with 100%
selectivity.
Herein, a CN supported Fe SAC (Fe1/CN) having a loading of
up to 11.2 wt% of Fe active sites was prepared via the
supermolecule method. Aberration-corrected high-angle annular
dark-field scanning transmission electron microscopy (AC-
HAADF-STEM) and X-ray absorption spectroscopy (XAS)
proved the single atom dispersion and highly uniform Fe-N4
centers of the Fe atoms in Fe1/CN. Qualitative and quantitative
analyses of the active species verified that Fe1/CN efficiently
activated PMS to generate 1O2 with 100% selectivity, which
1
from the catalytic activation of H2O2, to produce O2 is the most
commonly used method.[4] Unfortunately, the Haber–Weiss
•-
•
reaction (O2 + H2O2 → OH + OH- + O2) significantly reduces
the yield of 1O2.[5] To avoid this competitive reaction,
peroxymonosulfate (PMS) or peroxydisulfate (PDS) have been
used to generate 1O2 via self-decay, nucleophilic addition, and
1
catalytic activation.[6] However, the formation of O2 is generally
•
accompanied by the generation of free radicals such as OH and
•- [7]
1
SO4
.
And even the O2 is only a secondary active species.[8]
1
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10.1002/anie.202109488
Angewandte Chemie International Edition
COMMUNICATION
exceeds that of CN supported Fe nanoparticles (FeNP/CN), Co
SAC (Co1/CN), and Ni SAC (Ni1/CN) catalysts. The high
efficiency and selective generation of O2 from Fe1/CN activated
Fourier-transform extended X-ray absorption fine structure (FT-
EXAFS) spectrum (Figure 1f) of Fe1/CN exhibits a solitary peak
at approximately 1.7 Å, which is attributed to the Fe-N bond. In
comparison to Fe foil, FeO, and Fe2O3, no Fe-Fe or Fe-O peaks
were observed, indicating the absence of Fe clusters or oxides
in Fe1/CN. In the wavelet transform (WT) contour plots (Figure
S2), the intensity maxima of Fe foil at 7.9 Å-1 is attributed to Fe-
Fe bonds.[19] In addition, a solitary intensity maximum of Fe1/CN
at 4.2 Å-1 can be ascribed to the Fe-N bond.[20] The EXAFS-
fitting results show that the coordination number of Fe is 4
(Table S1, Supporting Information). All the above results confirm
that the Fe atoms in Fe1/CN are atomically dispersed in a Fe-N4
configuration (Figure 1g).
The effect of Fe1/CN activation on PMS was evaluated by the
degradation of organic pollutants. As shown in Figures 2a and
S3, Fe1/CN achieved the highest removal rate of 4-CP with a
Kobs of 0.55 min-1, which is 5.4, 1.7, and 6.5 times than that of
FeNP/CN, Co1/CN, and Ni1/CN, respectively. Total organic
carbon (TOC) test proved that the 4-CP was degraded into CO2
and H2O (Figure S4). In addition, other organic pollutants can
also be rapidly degraded (Figure S5). Fe1/CNs having different
Fe loadings exhibited volcano-like plots of the degradation rates
of 4-CP, with the maximum rate being obtained at the Fe content
of 7.0 wt% (Figure S6). Furthermore, Fe1/CNs having different
surface concentrations of Fe atoms but similar total Fe contents
were also used to degrade 4-CP (Figure S7 and Table S2).[21] As
shown in Figure S8, the rate of degradation of 4-CP increased
from 0.55 to 1.43 min-1 as the surface concentration of Fe atoms
increased. When CNs or no catalyst was added, 4-CP was not
removed in the PMS solution (Figure S9), indicating that the
expedited degradation of Fe1/CNs did not stem from the
enhanced surface area of CN. Therefore, the quicker
degradation of Fe1/CN was driven by the enhanced surface
concentration of Fe atoms.
1
PMS rapidly degraded p-chlorophenol (4-CP), and the optimized
apparent rate constants (Kobs) were as high as 1.43 min-1
(Equation. S1, Supporting Information). Compared with Co and
Ni sites, the density functional theory (DFT) calculations results
demonstrated that the Fe sites in Fe1/CN tend to adsorb the
terminal O of PMS, which can facilitate the oxidization of PMS to
form SO5•-, and thereafter efficiently generated 1O2 with 100%
selectivity. Because it solely produced 1O2, the Fe1/CN activated
PMS system exhibited strong resistance to interference from
anions, cations, and natural organic matter (NOM), and had a
wide pH tolerance and good cycle stability. This research opens
up a new avenue for the efficient activation of PMS and 100%
selective production of 1O2.
Figure 1. a) AFM and corresponding height profiles along the white line, b)
TEM, c) AC-HAADF-STEM, and d) EDX images of the Fe1/CN; e) normalized
Fe K-edge XANES and f) k3-weighted Fourier transform spectra of Fe foil, FeO,
Fe2O3, and Fe1/CN; and g) EXAFS fitting curve in R space (inset: structural
model of Fe1/CN, Fe: orange, N: blue, C: grey).
The Fe1/CN was synthesized by the supermolecule method
reported in our previous work with slight modification.[15] X-ray
diffraction (XRD) patterns and Fourier-transform infrared (FT-IR)
spectra exhibited the CN matrix of Fe1/CN (Figure S1,
Supporting Information).[16] No characteristic peaks associated
with Fe compounds were observed in Fe1/CN.[17] As shown in
Figure 1a and 1b, atomic force microscopy (AFM) and
transmission electron microscopy (TEM) images captured the
lamellar structure of Fe1/CN, which had
a thickness of
Figure 2. a) 4-CP degradation rate in different catalysts activated PMS
approximately 4 nm, and did not contain Fe nanoparticles.
Furthermore, AC-HAADF-STEM and energy-dispersive X-ray
(EDX) images demonstrated that all the Fe atoms (the bright
spots highlighted by orange circles) were atomically dispersed
on the CN support (Figure 1c and 1d).
systems; b) qualitative and quantitative analyses of active species present in
•
Fe1/CN activated PMS system; c) EPR spectra of OH, SO4•-, O2•-, and 1O2 in
Fe1/CN activated PMS systems; and d) the proportion of 1O2 in different
catalysts activated PMS systems.
As shown in Figure 1e, the absorption edge of Fe1/CN was
located between those of FeO and Fe2O3 in the Fe K-edge X-ray
absorption near-edge structure (XANES) spectra, indicating the
oxidation state of the Fe atom in Fe1/CN (Feδ+, 2 < δ < 3).[18] The
The effect of the state of the Fe species on PMS activation
was studied as well. In the homogeneous Fe2+ activated PMS
system, 4-CP was rapidly degraded in the first minute, however,
2
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10.1002/anie.202109488
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COMMUNICATION
and Ni1/CN, which were also SACs, for generating 1O2 by
activating PMS were approximately 49% and 27%, respectively
(Figures 2d and S24). Hence, Fe1/CN activated PMS system
produces solely 1O2, whereas FeNP/CN, Co1/CN, and Ni1/CN
also produce the SO4•-, •OH, 1O2, and O2•- active species.
its removal did not continue (Figure S10). Replenishing the Fe2+
content in the fifth minute permitted part of the remaining 4-CP
to be degraded, indicating that Fe2+ is consumed during the
activation of PMS.[22] Replacing Fe2+ using Fe3+ halted the
degradation of 4-CP. We infer that PMS is reduced by the Fe2+
to generate radical active species and Fe3+, and the generated
Fe3+ cannot be restored to Fe2+ for further activation of PMS
despite the presence of CN (Figure S11).[23] This indicate that
the strong interaction between CN and Fe plays important roles
in the continuous activation of PMS. Although homocatalysis is
generally more rapid than that via heterocatalysis, the Fe1/CN
heterocatalyst degraded 4-CP more rapidly than the
homogeneous Fe2+ in the PMS system did (Figure S12). In
summary, Fe1/CN combines the advantages of high efficiency
(of homocatalysis) and sustainability (of heterocatalysis),
achieving rapid and continuous activation of PMS for the
degradation of organic pollutant.
As shown in Figures S4 and S13, the rate of consumption of
PMS was more rapid than the degradation of 4-CP in the Fe1/CN
activated PMS system, indicating that the active species can be
rapidly and abundantly produced in the system. Nonetheless,
•
active species such as SO4•-, OH, O2•-, and high valent iron
(Fe(IV)) were not detected during the reaction (Figure 2b).
Specifically, the absorption intensity of nitro blue tetrazolium
(NBT) at 259 nm (the probe for O2•-) and the photoluminescence
(PL) intensity of 2-hydroxy terephthalic (TA-OH) at 425 nm (the
probe for •OH) remained constant throughout the reaction
(Figure S14).[24] Furthermore, when the hydroxybenzoic acid
(HBA) and methyl phenyl sulfoxide (PMSO) were used to probe
for SO4•- and Fe(IV), respectively, no singles corresponding to p-
benzoquinone (BQ) and methyl phenyl sulfone (PMSO2) were
recorded at the retention times of 5.0 and 9.5 min during the
reaction (Figure S15).[25] Furthermore, the scavengers of MeOH,
EtOH, KI, BQ, isopropanol (IPA), tert-butanol (TBA), superoxide
dismutase (SOD), and catalase (CAT) did not influence the
degradation rate of 4-CP (Figure S16), implying the absence of
Figure 3. a) Degradation rate of 4-CP by Fe1/CN activated PMS under
different atmospheres; b) EPR spectra for the detection of 1O2 in the presence
of TEMP and BQ using water as the solvent; c) LSV curves of Fe1/CN under
different conditions; d) the adsorption energies of PMS onto the different sites
of catalysts (inset: molecular model of PMS); e) evolution process of PMS into
SO5•- on Fe1/CN.
As shown in Figure 3a, the atmospheres (Ar, O2, or air) did not
influence the degradation rate of 4-CP, suggesting that the O for
1O2 was not derived from dissolved oxygen. As shown in Figures
3b and S16, the EPR singles strength of 1O2 continue to
increase and the degradation rate of 4-CP had no change in the
1
•-
present of BQ, indicating that O2 was not generated from O2
.
The aforementioned results indicate that Fe1/CN can efficiently
SO4•-, OH, and O2 active species. In addition, atrazine (ATZ)
and PMSO were not degraded by the Fe1/CN activated PMS
system (Figure S17), indicating the absence of •OH and
Fe(IV).[6a] When 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and
2,2,6,6-tetramethyl-4-piperidinyloxyl (TEMP) were employed to
•
•-
1
activate PMS to directly generate O2 while avoiding the Haber-
Weiss competitive reaction.[12c] In linear sweep voltammetry
(LSV) analyses (Figure. 3c), the current density of the Fe1/CN
electrode significantly increased in the presence of PMS, which
confirms that electrons transfer from PMS to the Fe single-
atoms.[11] As shown in Figure 3d and Table S3, the pyridine
nitrogen (pyr-N) site of Co1/CN adsorbed the O2 site of PMS and
the graphitic nitrogen (gra-N) site of Ni1/CN adsorbed the O1 site
•
capture the SO4•-, OH, O2•-, and 1O2, respectively, no electron
paramagnetic resonance (EPR) characteristic signals of DMPO-
•-
SO4•-, DMPO-•OH, and DMPO-O2 was recorded during the
reaction (Figure 2c).[26] Relatively, three characteristic peaks of
TEMP-1O2 were clearly detected in the EPR spectrum, and the
signal intensity continually increased during the reaction,
indicating that Fe1/CN can continuously activate PMS to form
1O2.[4b] When L-histidine, furfuryl alcohol (FFA), or NaN3 was
added, the degradation rate of 4-CP was sharply decreased,
and the inhibitory effect increases with increase in the dosage of
the scavengers (Figure S18), suggesting that 1O2 is the sole
•-
of PMS, which promoted the reduction of PMS to generate SO4
•
and OH. In addition, Fe nanoparticles in FeNP/CN preferentially
adsorbed the O2 site of PMS, which promoted the
•-
decomposition of PMS into SO4 and •OH via a completely
spontaneous process.[28] In contrast, Fe1/CN tends to adsorb the
O1 site of PMS on the Fe site, which promoted the oxidation of
•-
PMS to SO5 by the loss of the H atom (Figure 3e). Due to the
high reaction rate (~2 × 108 M-1 s-1) and low activation energy
1
•-
(7.4 ± 2.4 kcal mol-1), SO5 rapidly self-reaction to generate
active species. In addition, O2 remained the sole active species
-
S2O82-, SO4 , and 1O2 (Figure 3e and Equations 1-3).
regardless of the loading amount and surface exposure ratio of
•-
the Fe single-atoms in Fe1/CNs (Figure S19). However, the SO4
,
•-
HSO5- → SO5•- + H+ + e-
(1)
(2)
(3)
•OH, 1O2, and O2 active species were all detected in the
FeNP/CNs activated PMS systems (Figure S20), in line with the
SO5•- + SO5•- → S2O82- + 1O2
SO5•- + SO5•- → 2SO42- + 1O2
trapping tests (Figure S21). With the decrease of Fe sizes from
200 nm to single-atom, the generated proportion of 1O2
increased from 43% to 100% (Figures 2d, S22, and S23,
Equations S2-6).[27] In comparison, the selectivities of Co1/CN
3
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10.1002/anie.202109488
Angewandte Chemie International Edition
COMMUNICATION
stability and practical application prospect of Fe1/CN. This work
provides a new idea for selectively producing 1O2, which can
achieve highly selective degradation of pollutants in wastewater.
Acknowledgements
We gratefully acknowledge the financial support of the National
Natural Science Foundation of China (51868050, 51938007,
51720105001, and 51878325) and the Natural Science
Foundation of Jiangxi Province (20202BAB213011). The
synchrotron radiation experiment for XAFS was performed at the
BL14B1 of Japan Atomic Energy Agency with the approval of
JAEA and Japan Synchrotron Radiation Research Institute
(Proposal Nos. 2016B3618, 2018A3631).
Keywords: singlet oxygen • Fe single-atom catalyst • graphitic
carbon nitride • degradation • organic pollutants
Figure 4. 4-CP degradation rate in a) Fe1/CN activated PMS system in the
presence of different ions; b) Fe1/CN and FeNP/CN activated PMS systems at
different NOM concentrations; c) removal efficiency of 4-CP at different initial
pH; and d) the 4-CP degradation rate in different natural waters of Fe1/CN
activated PMS systems.
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-
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did not significantly influence the degradation rate of 4-CP at any
of the dosages tested. This indicates that the Fe1/CN activated
PMS undergoes less interference from common background
organic and inorganic substances present in water.[29] Moreover,
Fe1/CN could activate PMS for the degradation of 4-CP
effectively in the pH range of 3.4–10.8 (Figure 4c), which verifies
that Fe1/CN catalyst and 1O2 active species have strong
tolerance to the pH of the solution. In contrast, the rate of
degradation of 4-CP changed significantly when diverse anions,
cations, and NOM were introduced into the FeNP/CN activated
PMS system (Figures 4b and S26), which shows that the
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•-
degradation process of 4-CP with SO4 and •OH radicals is
easily disturbed by the environmental substances.[30] More
importantly, Fe1/CN achieved similar rates of degradation of 4-
CP in natural (tap water, the Poyang Lake water, and the
Yangtze River water) and deionized waters (Figure 4d),
indicating its excellent practical application prospects. As shown
in Figure S27, the cyclic tests demonstrated that Fe1/CN is more
stable than FeNP/CN during the activation of PMS for the
degradation of 4-CP. In summary, the Fe1/CN activated PMS
system exhibited excellent pH adaptability, inorganic ions, and
NOM interference tolerance, and stability.
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This work prepared Fe1/CN catalysts having a highly uniform
Fe-N4 structure using the supermolecule method. When Fe1/CN
1
was used to activate PMS, O2 active species was generated at
100% selectivity, which facilitated an extremely rapid 4-CP
degradation rate of 1.43 min-1. DFT calculations showed that the
Fe-N4 sites can adsorb the terminal O of PMS and then oxidized
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1
to SO5•-, and subsequently generate O2. Due to the generation
1
of O2 with 100% selectivity, the Fe1/CN activated PMS system
exhibits strong resistance to interference from environmental
media containing anions, cations, and NOM, and operates
efficiently in the wide pH range of 3–11. Furthermore, the cycle
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Entry for the Table of Contents
The carbon nitride supported Fe single-atoms catalyst (Fe1/CN) with a Fe loading of 11.2 wt% was developed to generate 100% 1O2
by activating peroxymonosulfate (PMS). The adsorption of terminal O and oxidation of PMS by Fe-N4 sites played the most important
roles for the generation of 1O2 with 100% selectivity. As a result, the Fe1/CN activated PMS system exhibited strong resistance to
various factors during the degradation of organic pollutants.
6
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