Advanced Materials - 2022 - Cheng - Site Specific Electron Driving Observations of CO2 To CH4 Photoreduction On Co Doped

Research Article
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Site-Specific Electron-Driving Observations of CO2-to-CH4

Photoreduction on Co-Doped CeO2/Crystalline Carbon
Nitride S-Scheme Heterojunctions
Lei Cheng, Xiaoyang Yue, Jiajie Fan, and Quanjun Xiang*
value-added C1 products induces com-

Photoexcited dynamic modulation, maximizing the effective utilization of plex electron–proton coupling reactions,
photoinduced electron–hole pairs, dominates the multiple electrons-involving which drives multiple electrons-involving
reduction pathways for terminal CH4 evolution during CO2 photoreduction. reduction pathways with a variety of
Yet, the site-specific regulation of directional charge transfer by modifica- C1 products, such as CO (two electron-
involved), HCHO (four electron-involved),
tion of an S-scheme heterojunction has seldom been discussed. Herein,
CH3OH (six electron-involved), and CH4
an atomic-level tailoring strategy by anchoring single-atomic Co into CeO2 (eight electron-involved).[4–7] Neverthe-
co-catalyst rather than carbon nitride supports, which can selectively favor less, the selectivity of these products is
CO2-to-CH4 photoreduction, is reported. Through in situ dynamic tracking heavily followed by various kinetic and
investigations, this study identifies that surface Co-embedded bimetallic CeCo thermodynamic parameters, leading to
conjunction is the key feature driving a strong interconnection of dynamical high conversion efficiency remain rare
at present.[8–10] Especially, owing to the
charge states through S-scheme heterojunctions. The Co-embedded modifica-
requirements of sustainable photoinduced
tion into CeO2 co-catalysts is demonstrated to have a critical effect on direc- electron input, effective photocatalysts for
tional charge control, accelerating the driving of electrons from the carbon selective CH4 production with high yield
nitride donations to site-specific Co hubs, which thereby promotes electronic are greatly intriguing but remains a huge
transferability for electrons-involving CH4 formation. As a result, an unprec- challenge.
By virtue of π-conjugated stacking
edented CH4 yield (181.7 µmol g−1) is obtained with a high turnover number
structure and intrinsic carrier delocaliza-
(411.4) through a fully gas–solid reaction, demonstrating its potential toward tion, poly(triazine imide) (PTI) has been
targeted CH4 formation without adding any sacrificial agent. considered as an ideal platform for coor-
dinating with suitable co-catalysts.[11,12]
This polymeric carbon nitride (PCN)
1. Introduction has ligand flexibility with regular atomic coordination,[13,14]
especially for a highly crystalline one, which enables molec-
Conversion of CO2 into hydrocarbon fuels via artificial photo- ular-level investigations on dynamic charge transfer across
synthesis is recognized as a key process to synchronously the interfacial configuration.[15,16] Particularly, direct integra-
address the greenhouse issue and global energy demand.[1–3] tion of PCN with metal oxide in heterogeneous photocatal-
Normally, photocatalytic CO2 reduction reaction (CO2RR) to ysis, including transition metal oxide (e.g., Co3O4,[17] ZnO,[18]
and CuO[19]), noble metal oxide (e.g., PdO,[20] RuO2,[21] and
L. Cheng, X. Yue, Q. Xiang
PtO2[22]), and rare earth oxide (e.g., CeO2[23] and La2O3[24]),
State Key Laboratory of Electronic Thin Film and Integrated Devices calls for useful strategy to facilitate the interfacial elec-
School of Electronic Science and Engineering tron modulation. Despite substantial efforts on developing
University of Electronic Science and Technology of China PCN-based heterogeneous composite for high CO2RR,[25,26] the
Chengdu 610054, P. R. China efficiency of photoinduced kinetic coupling, namely, charge
E-mail: xiangqj@uestc.edu.cn
transfer, is inherently short-term durability, which hampers
L. Cheng, X. Yue, Q. Xiang
Yangtze Delta Region Institute (Huzhou) the multiple electrons-involving reduction for terminal CH4
University of Electronic Science and Technology of China generation.[27,28] In this regard, exact regulation of PCN-based
Huzhou 313001, P. R. China heterogeneous photocatalysts for boosting directional charge
J. Fan transfer is one way to improve the selectivity control of CH4
School of Materials Science and Engineering versus other C1 products.
Zhengzhou University
Zhengzhou 450000, P. R. China
Coupling of isolated metal atoms into PCN by a well-
defined atomic coordination offers new opportunities for
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202200929. heterogeneous photocatalysts.[29,30] Among the alternatives,
low-cost and environmentally friendly transition-metal-based
DOI: 10.1002/adma.202200929 species is mostly desirable for anchoring in PCN supports
Adv. Mater. 2022, 34, 2200929 2200929 (1 of 11) © 2022 Wiley-VCH GmbH
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by a field confinement,[7,31] such as functionalized Co single- 2. Results and Discussion

atom catalysts.[32] However, the direct atomic Co-anchoring
into co-catalysts has rarely been studied for those emerging 2.1. Structure Sensitivity of CeCo-PTI
PCN-based S-scheme heterojunction photocatalysts towards
CO2RR. Meanwhile, quantitative track of the number of elec- Distinct metal–support configuration with desirable electronic
trons transferred in S-scheme heterojunction also face issues modulation can be achieved by anchoring single metal atoms
regarding structure-property correlation, which is largely into host catalysts.[33,34] In this way, integrating isolated Co
underexplored experimentally. atoms into highly crystalline PTI over a binary CeO2 co-catalytic
In this work, we demonstrate an atom-specific bimetallic co- system could be feasible, of which the CeO2 co-catalyst can
catalyst regulation by introducing atomically Co-doped CeO2 be of an assistant for promoting dynamic reactions in heteroge-
into highly crystalline PTI (CeCo-PTI) for CO2 photoreduc- neous photocatalysis. However, we find that the Co atoms are
tion to CH4. We focus on atomic-level tailoring of bimetallic incorporated into CeO2 nanoparticles rather than the PTI sup-
CeCo co-catalysts that feature functionalized Co species for ports during an in situ grown procedure (as shown in Figure 1).
directional electron transfer channels via S-scheme het- To investigate this, three types of heterogeneous composites
erojunctions during the photocatalytic process. A series of were synthesized with and without doping Co or PTI precursors,
tracking characterizations, including in situ CO2-diffuse which designate as CeO2/PTI (Figure 2a, Ce-PTI), Co-doped
reflectance infrared Fourier transform spectroscopy (CO2- CeO2 (Figure 2b), and CeCo-PTI (Figure 2c), respectively, as
DRIFTS), femtosecond time-resolved transient absorp- well as pure highly crystalline PTI (Figure S1, Supporting Infor-
tion spectroscopy (fs-TA), aberration-corrected high-angle mation) and Co3O4 (Figure S2, Supporting Information). For
annular dark-field scanning transmission electron microscope Ce-PTI, the distinct lattice spacing of CeO2 corresponds to the
(AC HAADF-STEM), and X-ray absorption spectroscopy dominant (111) and (200) facets with typical single-crystal pat-
(XAS), are operated for dynamic identification across the fine- tern by fast Fourier transform (FFT) (Figure 2d and Figure S3,
tune interaction. To further substantiate the distinctive mech- Supporting Information).[23,35] Particularly, we demonstrate
anistic details, we performed density functional theory (DFT) the lattice fringe of CeO2 nanoparticles among Co-doped CeO2
calculations to understand the electronic transferability and (Figure 2e and Figure S4, Supporting Information) and CeCo-
confirm the site-specific electron-driving effect between atom- PTI (Figure 2f) are significantly changed by introducing the Co
ically bimetallic CeCo co-catalysts and PTI. Most notably, this species. This could be ascribed to the high surface free energy
paradigm exhibits successful selectivity control of CH4 evolu- of isolated Co atoms and strong coulomb force between Co2+
tion (rate: 181.7 µmol g−1; selectivity: 88.3%), which is even and (Ce(NO3)6)2− precursors. Alternatively, the existence of CeO2
31-fold and 121-fold higher than those of Ce-PTI (5.8 µmol g −1) is more available than PTI for trapping single-atomic-site Co,
and PTI (1.5 µmol g−1). To our knowledge, this extraordinary showing the regularly Co-doped CeO2 composite. The crystalli-
CH4 yield is unprecedented among the reported co-catalyst- zation characteristics of CeO2 converted by doping Co atoms are
induced PCN photocatalysts through gas–solid reactions also similar to those of the metal-incorporating CeO2 catalysts
without adding any sacrificial agent. (e.g., Ti-doped CeO2,[36] Co-doped CeO2,[37] and Pt-doped CeO2[38]).
Figure 1. Schematic for well-defined photocatalytic platform by integrating Co-doped CeO2 nanoparticles with highly crystalline poly (triazine imide),
PTI. Left: structure model of the nanocrystal composite with Li+/Cl− intercalation omitted for clarity. Right: proposed dynamic charge-transfer mecha-
nism, with the corresponding active species and surface-bound interaction (η1 and η2 mark electron transfer and trapping across surface Co-embedded
CeCo conjunction). Color scheme: Co, green; Ce, blue; O, red; C, gray; and N, white.
Figure 2. The morphology and structure of Co-doped CeO2 nanoparticles. a–c) Crystallization simulation for CeO2 (a), Co-doped CeO2 (b), and CeCo-
PTI (c). Color scheme: Ce, red; O, gray; Co, blue. d–f) HRTEM images of CeO2/PTI composite (Ce-PTI) (d), Co-doped CeO2 (e), and CeCo-PTI (f).
With the expanded view of the red rectangles in the right top and the corresponding FFT images in the right bottom. g,h) STEM and i) TEM images
of CeCo-PTI.
2.2. Structural Characterization of CeCo-PTI The X-ray diffraction (XRD) patterns show a typical diffrac-
tion with strong reflection indexed as (100) among PTI, Ce-PTI,
We performed spatially resolved morphology visualization onto and CeCo-PTI, representing the in-planar tri-s-triazine unit of
CeCo-PTI by using a series of low- and high-resolution elec- carbon nitride,[39] which is different from the bulk carbon nitride
tron microscopy characterizations. 2D nanorod structures are (Figure S6, Supporting Information). The additional peaks of
observed for CeCo-PTI (Figure 2g–i and Figure S5a,b, Sup- Ce-PTI and CeCo-PTI are indexed to the cubic CeO2 with no
porting Information), which are identified for the formation findings of Co species as the minor doping. However, the cor-
of polymeric carbon nitride, similar to that of pure PTI responding XRD pattern in Figure S7 (Supporting Information)
(Figure S1, Supporting Information). Moreover, isolated bright shows that the diffraction peak of Co-doped CeO2 belonged to
contrast spots are well dispersed to the PTI supports with the CeO2 (111) is shifted at a higher angle by the introduction of Co
nanoparticle size regime of 2–3 nm. Energy-dispersive X-ray spec- species. This slight lattice shrinking verifies the deformation
troscopy (EDS) mapping analysis (Figure S5d, Supporting Infor- of CeO2 lattice framework by successfully embedding with Co
mation) demonstrates the distribution species onto CeCo-PTI atoms.[40] UV–vis DRS spectra illustrates that Co-doped CeO2
composed of Ce and Co atoms, of which the loading content are exhibits significantly enhanced light absorption intensity with
29.9 and 4.2 wt%, respectively, as measured by inductively cou- a band energy (3.18 eV) in comparison with pure CeO2, which
pled plasma-mass spectrometry (ICP-MS) (inset of Figure S5a, further indicates the band alignment in the intrinsic structure
Supporting Information). AC HAADF-STEM images display of CeO2 when loading with Co atoms (Figure S8a, Supporting
both Co-doped CeO2 nanoparticles and highly crystalline PTI Information).These observations are also proved by X-ray photo
(Figure 3a,b), and the latter shows typical lattice fringes of 0.33 nm electron spectroscopy (XPS), of which binding energies for
corresponding to the (002) plane of graphitic carbon nitride.[11] typical spin–orbit doublets of Ce 3d over CeCo-PTI are shifted
Figure 3. Morphology and structure characterizations. a,b) Aberration-corrected HAADF-STEM images of CeCo-PTI. The structure model of
CeCo-PTI is shown at the bottom right. c) XRD patterns of PTI, Ce-PTI, and CeCo-PTI. d) XPS spectra of Ce 3d for CeCo-PTI (top) and Ce-PTI (bottom).
e) Normalized XANES spectra at Co K-edge of CeCo-PTI with Co foil, CoO, CoPc, and Co3O4 as references. f) Wavelet transform (WT) contour plots
of CeCo-PTI (left) and Co3O4 (right).
to the high-binding-energy side (Figure 3d), implying the for- X-ray absorption near-edge structure (XANES) curves illustrate
mation of relatively spin–orbit coupling between Ce and Co the chemical state of Co species among CeCo-PTI and a series
atoms.[41] of reference samples. The intensity position of absorption edge
for CeCo-PTI (inset of Figure 3e) is located between that of CoO
and Co3O4, implying a positively valence state of Co between
2.3. Determination of Co Atom Immobilization Co2+ and Co3+.[42,43] The wavelet transform (WT) contour plots
show the CeCo-PTI possesses a dominant peak at ≈1.5 Å
To uncover the local atomic coordination among Ce and Co (Figure 3f), which corresponds to CoO bonds. Specially, char-
species, we performed the X-ray absorption spectroscopy (XAS) acteristic signals at ca. 2.5 Å of CeCo-PTI are observed with
measurements of Co K-edge for CeCo-PTI (Figure 3e,f and slight deformation compared as that of Co3O4 (Figure 3f),[43]
Figure S9, Supporting Information). As shown in Figure 3e, suggesting the spatial Co species are of field confinement for
the formation of Ce-Co doping-intercalation sites. Moreover, (Figure 4b), respectively. As shown in Figure 4a, two main
the curve-fitting analysis in the R space of Fourier-transformed white-line absorption edge diagnostic of Ce L3-edge around
extended X-ray absorption fine structure (EXAFS) for CeCo-PTI ≈5730.3 and 5737.4 eV is identified in CeCo-PTI. These double
shows the prominent bonding configuration (Figure S10, absorption edges are described into a transition from Ce 2p3∕2
Supporting Information) with the fitted parameters listing in to the unoccupied Ce 5d state mixed with Ce 4f1 and Ce 4f° final
Table S1 (Supporting Information). In comparison with pure states,[44] suggesting the fluctuation among the Ce3+/Ce4+ oxida-
Co3O4, a shifted scattering paths is identified in CeCo-PTI tion state. For qualifying the ground-state electronic configura-
(Figure S10, Supporting Information), which could be attrib- tion, we present a curve fitting of Ce L3-edge in the XANES,
uted to crystal reregulation of Co sites toward higher charge which consists of four components recorded as A, B, C and D.
density modulation. Features A and B are classified into the multi-electron configu-
To further verity the atomic interaction by the direct field ration between 2p and unoccupied Ce 5d orbits of Ce, accom-
confinement, the coordination environment of Ce L3-edge in panied by the interaction of excited charge carriers.[45] The low-
CeCo-PTI is also conducted via XANES (Figure 4a) and EXAFS energy shoulder of D is assigned as the dipole-forbidden 2p–4f
Figure 4. Experimental XAFS measurements and theoretical calculation of CeCo-PTI. a) Normalized XANES spectra at Ce L3-edge of CeCo-PTI with
fitting result of four individual components (A, B, C, and D). b) Fourier-transformed EXAFS spectra of CeCo-PTI with CeO2 as reference. The inset
shows the upshift scattering path at the second shell in CeCo-PTI. c) Wavelet transform (WT) contour plot of CeCo-PTI. d) The electrostatic potentials
of PTI, CoO2, and Co-doped CoO2. Φ is work function. e) Schematic illustration of internal electric field (IEF)-induced charge modification and the
formation of S-scheme heterojunction of CeCo-PTI. EVAC and Ef are vacuum and Fermi levels, respectively. CB and VB are conduction band and value
band, respectively. f) The charge accumulation surrounding Co core through 3D difference charge density (left, green isosurface: electron depletion;
yellow isosurface: electron accumulation) and 2D valance charge density (right) in Co-doped CeO2. g) Electron orbital distribution of Ce in CeO2 and
Co-doped CeO2, respectively.
transition, along with the 5d split in the evolving local struc- directly interfacial configuration allowing the photogenerated
ture in C. The continuum resonance (CR) of CeCo-PTI (inset electrons transfer is also confirmed through the Mott–Schottky
of Figure 4a) is determined by a combination of CeCo scat- tests (Figure S13, Supporting Information). The positive Mott–
tering, which could be as arising from the independent of the Schottky plots suggest that both PTI and Co-doped CeO2 are
Co doping.[46] n-type semiconductors. According to the Kubelka–Munk func-
The EXAFS of CeCo-PTI shows scattering paths of Ce centers tion, we demonstrate that the calculated conduction band
in R space with the comparison of pure CeO2 (Figure 4b). We potential (ECB) of PTI is determined as −0.72 V (vs NHE),
demonstrate that both main features are observed among CeCo- which is more positive than Co-doped CeO2 (−1.19 V vs NHE).
PTI and CeO2, relating to the CeO coordination at ≈1.9 Å. Such formed heterojunctions drive the charge transfer in an
The results are also supported by the curve-fitting analysis of S-scheme mode, thus promoting the effective utilization of
EXAFS (Figure S11 and Table S1, Supporting Information). photoinduced electrons in the multiple electrons-involving
Notably, CeCo-PTI displays a fingerprint information at second reduction pathways for CH4 and CO evolution.
peak associated with a longer shifted bond distance, corre- To further unravel the photogenerated charge transfer
sponding to the redistributed crystal structure, which could dynamics and preliminary functionalization of Co state, a
be a consequence of CeCo bond formation. The WT contour converged site-specific electron-driving mechanism is carried
plot shows the maximum radial distance of CeCo-PTI is around out based on the determined CeCo-PTI nanocrystal structure.
≈1.5–2.5 Å−1, corresponding to CeO bond with CeCo bond The electron-driving observations are supported by the charge
in higher R-region, as illustrated in Figure 4c. accumulation surrounding Co core through 3D difference
charge density and 2D valance charge density in CeO2-111-Co-3
(Figure 4f). The atom-specific Co species induces the dynami-
2.4. Site-Specific Observations of Dynamic Charge Separation cally interconnected electronic properties through local CoO
bonding, suffering from high surface-free-energy and coordina-
Upon acquiring the structural configuration of CeCo-PTI at the tion unsaturation, which drives the Co destabilization state for
atomic level, we process in-depth analysis of the site-specific directional charge transmission across heterogeneous interface
Co on intriguing electronic modulation using density func- from PTI. An electronic degeneracy of Ce in CeO2-111 and CeO2-
tional theory (DFT) calculations. As shown in Figure S12 (Sup- 111-Co-3 consisting of 5d, 4f, 3d, and 2p as well as valence state
porting Information), we demonstrate that a fully optimized (v) is given in Figure 4g. Notably, in comparison with CeO2, a
CeO2 (111) model (CeO2-111), with a theoretical stability by low partial overlapped characteristics between Ce 5d/4f-orbitals
index surface,[47,48] is performed as the surface-induced slab and Co 3d-orbitals emerge in CeO2-111-Co-3 nearby the Ef, sug-
for Co-embedded modification. In comparison with surface gesting an effective spin–orbit coupling hybridization across of
Co-embedded geometries into single O hollow site nearby O Ce centers by inducing the Co configuration. Moreover, com-
(CeO2-111-Co-1) and nearby Ce (CeO2-111-Co-2), the strongest pared with CeO2-111, the shifted density states in CeO2-111-Co-3
binding energy of couple field configuration is found for CeO2- (Figure S14, Supporting Information) by Co embedding further
111-Co-3, where both two Co atoms are embedded into O hollow identifies the direct orbital contribution of Co states combining
sites nearby the O site. We identify that it is the lattice destabi- with unoccupied Ce electron orbitals, bridging the electron
lization structure and the dimeric-valence-state Ce (Ce3+/Ce4+) injection to atomic Co centers.
that may lead to reconstruction of well-ordered Co-doped CeO2. Moreover, we performed series of elaborate measurements
The single Co core versus three Ce sites is of the incorpora- on quantify the charge-enriched driving in the bimetallic
tion of CeCo composite, altering the electronic properties and CeCo-PTI from the experimental side. As shown in Figure S15
local crystallinity in CeO2, which is consistent with results of (Supporting Information), high-resolution XPS spectra of N 1s
nanocrystalline redistribution of Co-doped CeO2 in Figure 2e. and Ce 3d for PTI and CeCo-PTI were performed in darkness
In addition, work function (Φ), as the efficient characteristics and under light irradiation. In comparison with pure PTI, we
for electrostatic interaction, is estimated from the energy dif- indicate that the peaks corresponded to sp2-hybridized N atoms
ference of vacuum and Fermi levels based on calculated elec- (CNC) and bridging N atoms (N(C)3) for CeCo-PTI shifted
trostatic potential.[3] The theoretical calculations show that Φ to lower binding energy in darkness and higher binding energy
value of PTI, CeO2, and Co-doped CeO2 is of 5.83, 6.67, and under light irradiation, suggesting the N elements work as the
3.52 eV, respectively (Figure 4d). The lower Φ of Co-doped CeO2 electron acceptor without irradiation but electron donor under
than that of CeO2 indicates that the Co-embedded modification irradiation. Inaddition, the characteristic signal peaks of Ce
into CeO2 co-catalysts definitely changes electron configura- 3d for CeCo-PTI shifted to low binding energy under irradia-
tion, shifting the Fermi level (Ef ) toward conduction band (CB) tion, implying it acts as the electron acceptor after light activa-
minimum of CeO2. Moreover, the larger Φ of PTI (5.83 eV) tion.[49] Such charge transport improvement was also proved
indicates that PTI has lower Ef than Co-doped CeO2 (3.52 eV). by the measurement of electron paramagnetic resonance
Based on the thermodynamic distribution, the higher Ef of Co- (EPR) measurements (Figure S16, Supporting Information).
doped CeO2 enables internal electric field (IEF) driving from Besides, as shown in Figure S17 (Supporting Information), a
the site-specific Co-doped CeO2 to carbon nitride for enabling typical characteristic PL signal is observed for all as-synthesized
the same Ef (After contact as shown in Figure 4e). This electron photocatalysts, illustrating the radiative recombination of the
modulation by the interfacial IEF and bent band drives a strong photogenerated electron–hole pairs of PTI at around 460 nm
interconnection for subsequent directional charge transfer (consistent with the bandgap of PTI (≈2.7 eV in Figure S8b,
from the PTI to Co-doped CeO2 under light irradiation. This Supporting Information]). There are strong quenching of
PL for CeCo-PTI and Ce-PTI, implying that both the introduc- range of 500–600 and 670–700 nm, which would be ascribed
tion of Co-doped CeO2 and CeO2 could efficiently suppress to the absorption of excited states and photoproduct, respec-
the radiative recombination in PTI.[50,51] This emerging non- tively, as the decay kinetics of photogenerated charge carriers in
radiative pathway of photoexcited carriers across the surface CeCo-PTI. For further uncover the electron-transfer kinetics over
heterojunctions of CeCo-PTI and Ce-PTI also exhibits across CeCo-PTI, three dynamical decay traces are acquired by probing
the fine-tune interaction, being confirmed by the measurement at 450, 500, and 560 nm (Figure 5c), of which the bi-exponential
of a decreased average lifetime[52] (2.88 ns for CeCo-PTI and fitting recovery features are spread out in the inset of Figure 5c.
2.78 ns for Ce-PTI as comparison with PTI (10.59 ns) (as shown The representative build-up delayed by up to hundreds of nanosec-
in Table S2, Supporting Information). More importantly, as onds (e.g., 132–270 ps in the CeCo-PTI system) reflects the initial
comparison with Ce-PTI, the higher electron transfer rate con- exciton cooling of catalysts.[53] The following recovery (≈3–6 ps)
stant (Ket) of CeCo-PTI (1560.3 s−1) are identified as shown in is essentially traced to the photogenerated electron trapping
Figure S18 and Table S2 (Supporting Information), which through intrinsic shallow states in CeCo-PTI. Notably, the ultra-
reveals a strongly electron-driving effect from PTI to CeO2 by fast decay kinetics with a time of ca. 0.4 ps is identified, reflecting
the introduction of site-specific Co species.[16] the fast photoinduced electronics migration in CeCo-PTI.
Figure 5b displays fs-TA absorption spectra of CeCo-PTI This fast exciton relaxation (<1 ps) further reveals the facilitated
consist of various time delays irradiated with pulse at 350 nm. electron trapping by the Co centers near the interfacial configu-
Broad absorption signals decrease from 5.3 to 1900 ps in the ration of CeCo-PTI,[29,54,55] consistent with the DFT analysis.
Figure 5. Decay lifetime observation for dynamic charge separation in CeCo-PTI. a) Time-resolved transient PL decay of PTI, Ce-PTI, and CeCo-PTI.
b) Femtosecond TA spectra of CeCo-PTI at different probe delays under 350 nm excitation. The inset shows interfacial electronic modification in CeCo-
PTI. c) TA kinetic traces of CeCo-PTI probed at 450, 500, and 560 nm, respectively. d) Schematic of decay lifetime on CeCo-PTI by the combination of
time-resolved transient PL and Femtosecond TA measurements.
2.5. Monitoring Dynamic CO2 Conversion (ν(CO) of formaldehyde: 1108 cm−1; σ(CH2) of formaldehyde:
by In Situ CO2-DRIFTS 1504 cm−1)[57] and formic acid (COOH*: 1618 cm−1)[58] are also
observed in the dark, followed by introducing the gas mixtures.
In situ DRIFTS is used to elucidate dynamic mechanism of The smooth baseline before introduction of the gas mixtures
CO2 photoreduction to CH4 through surface adsorption and rules out the possibility of the hydrocarbon species on the
activation. The CO2-derived intermediates onto CeCo-PTI are surface of the materials. Therefore, the characteristic signal
dynamically detected during the in situ photocatalytic process of these hydrocarbon species may be driven by the free OH
by introducing continuous-flow CO2/H2O reactants (details as groups and active surface oxygen groups onto CeCo-PTI, thus
shown in the Supporting Information). Two sequential proce- resulting in the formation of hydrocarbon species in the dark.
dures, namely, surface adsorption process and photocatalysis Furthermore, the characteristic vibration also dynamically
process, are carried out in the dark (Figure S20a, Supporting recorded to evaluate the surface-adsorbed species and interme-
Information, background subtracted prior to CO2 adsorption) diates under light irradiation (from 0 to 120 min). As shown
and under light irradiation (Figure 6 and Figure S20b, Sup- in Figure 6, various vibrational features with absorption bands
porting Information), respectively. Prior to illumination, sev- of hydrocarbon group, including HCO3* (1200 cm−1)[56,58] and
eral time-resolved features assigned to bicarbonate (HCO3*: CHO* (1102 cm−1,[57] and 1165 cm−1[58]) are observed in CeCo-PTI,
1654 and 1206 cm−1, symmetric stretching: 1427 cm−1; σ(OH) as well as the presented monodentate carbonate (m-CO32−:
bending vibration: 1254 cm−1),[56] and bidentate carbonate 1312 cm−1)[56] and carboxylate (CO2−: 1266 and 1284 cm−1) spe-
(b-CO32−: 1355 cm−1),[56] are identified (Figure S20a, Supporting cies.[58,59] Notably, the absorbed intensities assigned to char-
Information). The intensities of these characteristic vibration acteristic vibration of hydrogenation species are significantly
peaks are increased gradually with a prolonged adsorption time reduced with the extension of light irradiation, suggesting that
from 0 to 60 min, suggesting the distinct intermediate bonding CeCo-PTI is more inclined to protonate CO* to hydrogena-
interaction is driven by combination of adsorbed CO2 on the tion species rather than dissociate CO* intermediates from the
surface of CeCo-PTI.[57] It should be pointed out that CHO* bound surface. The CeCo-PTI presents an elementary hydrogen-
ation reaction pathway for CH3O* formation (1053 cm−1).[57] The
remarkable adsorption signal of CH3O* intermediates demon-
strate that CeCo-PTI is of high capability for the desirable proto-
nation pathways, which plays vital role for CO2 photoreduction
into hydrogenation steps, followed by dissociation of terminal
CH4 on account of directionally consumed CH3O* species
(CO2 → CO32− → COOH* → CHO* → CH3O* → CH4).[16,29]
Furthermore, the decreased characteristic CO2 adsorption
band as shown in Figure S20b (Supporting Information)
(3300–3600 cm−1) further demonstrates the efficiently kinetic
transformation of CO2 involving in light-driven CO2 reduction.
In this regard, the well-regulated CeCo-PTI exhibits favorable
conversion efficiency by the boosted electronic-driving force for
enhancing the terminal CH4 production.
2.6. Evaluation of CO2RR Activity
The photocatalytic performance of CO2 conversion among

CeCo-PTI and comparative Ce-PTI and PTI samples were con-
ducted toward the quantification of determined CH4 versus CO
products along a whole photocatalytic cycle. As shown in Figure 7a,
CeCo-PTI exhibits a remarkable CH4 yield by the introduction
of CeCo co-catalysts, and the photocatalytic rate reaches up to
above 181.7 µmol g−1 after light irradiation for 4 h, which is even
31-fold and 121-fold higher than those of Ce-PTI (5.8 µmol g−1)
and PTI (1.5 µmol g−1), respectively. Meanwhile, the gradually
increased CO yield of CeCo-PTI is also presented with a pro-
longed photocatalytic time to 4 h, giving the CO generation
rate up to 95.9 µmol g−1, nearly threefold and sixfold higher
than those of Ce-PTI (37.5 µmol g−1) and PTI (17.4 µmol g−1)
(Figure 7b). For further uncover the direct electronic metal–
support modulation, Co-doped CeO2 and pure CeO2 are also
Figure 6. In situ DRIFTS spectra for monitoring CO2-derived intermedi-
ates on CeCo-PTI during photocatalytic reactions. The adsorbed species served as target catalysts for evaluating the intrinsic photocata-
and intermediates are dynamically recorded every 20 min in gas mixtures lytic activity of CO2 conversion. Surprisingly, we demonstrate
consisting of CO2 and H2O vapours under light irradiation. only a small amount of CH4 and CO evolution is identified
Figure 7. CO2 photoreduction performance. a) CH4 and b) CO yield of CeCo-PTI, Ce-PTI, PTI, Co-doped CeO2, and CeO2 by recording every 30 min upon
illumination for 4 h. c) CH4 and CO evolution rate of as-synthesized photocatalysts, along with the equivalent electron consumption. d) CH4 and CO
selectivity of as-synthesized photocatalysts. e) GC-MS spectrum of the gas-phase products driven for CeCo-PTI in the photocatalytic reduction of 13CO2.
across Co-doped CeO2 (CH4: 2.4 µmol g−1; CO: 7.6 µmol g−1) selectivity is carried out as shown in Figure 7d. The active
and pure CeO2 (CH4: 1.2 µmol g−1; CO: 5.1 µmol g−1), which CeCo-PTI displays the highest CH4 selectivity of 88.3%, much
further confirms the atom-specific function for enhancing the higher than those of Ce-PTI (38.4%), PTI (25.0%), Co-doped
photocatalytic performance between Co and CeO2 onto PTI CeO2 (55.7%), and CeO2 (49.0%). These observations above
supports. further reveal that CeCo-PTI with atomic Co configuration ben-
In addition, the photocatalytic efficiency for CO2 reduction is efits the selectivity control of reduction products, featureing the
obtained by taking account of average output for 1 h (Figure 7c). functionalized Co-doped species inside CeO2 for prompting
A highest conversion efficiency is presented for CeCo-PTI, dynamic carrier mobility, especially for the hydrogenation reac-
namely, 45.4 µmol g−1 h−1 for CH4 and 24.0 µmol g−1 h−1 for CO, tion to CH4.
of which both the product is much higher than those of Ce-PTI The evolved CH4 and CO from distinct origin of carbon
and PTI. Moreover, we also summarized the photocatalytic effi- sources is analyzed through isotope tracking by using
ciency of CO/CH4 yield of other carbon-nitride-based photocat- 13C-labeled CO isotopic experiment. Given the 13CO atmos-
2 2
alysts as for comparison (seen as Table S3, Supporting Informa- phere as the ascertained photoreduction reactant, we have
tion). Note that the comparable activity and selectivity of CH4 investigated the carbon sources of terminal CH4 and CO prod-
generation is achieved by using the as-synthesized CeCo-PTI in ucts for excluding the decomposition of contaminated carbon
this work, higher than in the case of carbon-nitride-based pho- from polymeric carbon nitride. As shown in Figure 7e, the char-
tocatalysts. Quantitative equivalent electrons are also calculated acteristic fingerprints of m/z = 17 (13CH4) and m/z = 29 (13CO)
for each synthesized photocatalyst based on electron consump- are presented along the 13C-labeled CO2 reduction with nonla-
tion of CH4 and CO generation. The CeCo-PTI system exhibits beled exclusive peaks for the production of CH4 and CO prod-
a highly turnover number of effective reacted electron for ucts in CeCo-PTI, which implies the determined CH4 and CO
411.4 without the addition of any sacrificial reagent, rivaling the are stemmed from photocatalytic CO2 conversion.[60] Since no
significantly promoted electron toward CH4. Given the photo- external sacrificial agents were added in photocatalytic reac-
generated carriers involving in the hydrogenation reactions tion system, the evaluation of oxidation half-reactions are also
versus competing CO dissociation, the calculation of product tracked, along with production of oxygen from water oxidation
during the photocatalytic process (Figure 7e). This oxidation Keywords

half-reactions provides significant H+ for participating in CO2
bimetallic co-catalyst regulation, CO2-to-CH4 photoreduction, crystalline
reduction, revealing the mechanistic insights into CH4 evo- carbon nitride, directional charge transfer, S-scheme heterojunctions
lution through the subsequent hydrogenation reactions.[16]
Moreover, the control experiments also indicates that there is Received: January 27, 2022
no detectable signal for CO and CH4 production without photo- Revised: April 8, 2022
catalysts, CO2, H2O or light irradiation (Figure S21, Supporting Published online: June 2, 2022
Information).
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Advanced Materials - 2022 - Cheng - Site Specific Electron Driving Observations of CO2 To CH4 Photoreduction On Co Doped

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Advanced Materials - 2022 - Cheng - Site Specific Electron Driving Observations of CO2 To CH4 Photoreduction On Co Doped

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Research Article

Site-Specific Electron-Driving Observations of CO2-to-CH4

value-added C1 products induces com-

by a field confinement,[7,31] such as functionalized Co single- 2. Results and Discussion

2.6. Evaluation of CO2RR Activity

The photocatalytic performance of CO2 conversion among

during the photocatalytic process (Figure 7e). This oxidation Keywords

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