Efficient Photocatalytic Nitrogen Fixation over Cu#

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Efficient Photocatalytic Nitrogen Fixation over Cuδ+-

Modified Defective ZnAl-Layered Double Hydroxide
Nanosheets
Shuai Zhang, Yunxuan Zhao, Run Shi, Chao Zhou, Geoffrey I. N. Waterhouse,
Li-Zhu Wu, Chen-Ho Tung, and Tierui Zhang*
new strategies for enhancing N2 adsorp-

The photocatalytic reduction of nitrogen (N2) with water (H2O) as the tion, N2 activation, and electron transfer
reducing agent holds great promise as a sustainable future technology for kinetics during the photocatalytic reaction
the synthesis of ammonia (NH3). Herein, the effect of oxygen vacancies and to achieve the required step-change
improvements in NH3 production rates.
electron-rich Cuδ+ on the performance of zinc-aluminium layered double Oxygen vacancies (Vo) have been proved
hydroxide (ZnAl-LDH) nanosheet photocatalysts for N2 reduction to NH3 to be highly effective in promoting N2
under UV–vis excitation is systematically explored. Results show that a photofixation by boosting the charge
0.5%-ZnAl-LDH nanosheet photocatalyst (containing 0.5 mol% Cu by metal separation/transfer, optimizing optical
basis) affords a remarkable NH3 production rate of 110 µmol g−1 h−1 and properties of photocatalysts, lowering the
reaction energy barrier, hence optimizing
excellent stability in pure water. The X-ray absorption spectroscopy, electron
the reaction kinetics.[1a] Further, the
paramagnetic resonance, and density functional theory calculations reveal presence of Vo gives rise to unsaturated
that Cu addition imparts oxygen vacancies and coordinatively unsaturated metal sites with electron-rich proper-
Cuδ+ (δ < 2) with electron-rich property in the ZnAl-LDH nanosheets, ties, which similarly play a key role in
both of which readily contribute to efficient separation and transfer of catalytic process.[1b] The nonprecious 3d
photogenerated electrons and holes and promote N2 adsorption, thereby both transition metals (3d TMs) have been
investigated in this regard.[1c,d] Recent
activating N2 and facilitating its multielectrons reduction to NH3. theoretical and experimental results have
demonstrated that low-valence 3d TMs
derived from Vo with peculiar electronic
Currently, there is enormous interest in the development structures (such as Ti (III),[2] Mn (III),[3] Ni (I),[4] and Zn (I)[5])
of efficient semiconductor photocatalysts for the reduction are advantageous in promoting the adsorption and activation
of dinitrogen (N2) to ammonia (NH3) using water (H2O) as of reactants on the surface of catalysts, thereby enhancing
the reducing agent under mild conditions. Current rates of catalytic performance.[6] In photocatalysis, low-valence electron-
photocatalytic ammonia synthesis are far too low to warrant rich 3d TMs similarly act as catalytic centers or promoters to
serious practical interest, motivating researchers to explore enhance the kinetics of various thermodynamically unfavorable
reactions,[7] including organic synthesis,[8] water splitting,[9]
carbon dioxide reduction,[10] and organic pollutant degrada-
S. Zhang, Y. Zhao, Dr. R. Shi, Dr. C. Zhou, Prof. L.-Z. Wu, tion.[11] Among these electron-rich 3d TMs, low-valence Cuδ+
Prof. C.-H. Tung, Prof. T. Zhang (0 < δ < 2) demand particular attention.[12] Most work to date
Key Laboratory of Photochemical Conversion and Optoelectronic
Materials relating to low-valence Cuδ+ in photocatalytic applications has
Technical Institute of Physics and Chemistry been focused on Cu2O-related materials,[13] Cu organic com-
Chinese Academy of Sciences plexes,[14] and Cu-doped TiO2.[15] However, the low-valence
Beijing 100190, China Cuδ+ existing in these materials are generally unstable during
E-mail: tierui@mail.ipc.ac.cn
photocatalytic reactions, easily being transforming into other
S. Zhang, Y. Zhao, Prof. T. Zhang
Center of Materials Science and Optoelectronics Engineering
Cu species (such as Cu0) with totally different function in
University of Chinese Academy of Sciences photocatalytic reactions (e.g., Cuδ+ is typically an electronic or
Beijing 100049, China structural promoter in photocatalyst systems, whereas Cu0 gen-
Prof. G. I. N. Waterhouse erally acts as a cocatalyst).[16] This makes understanding of the
School of Chemical Sciences role of low-valent Cuδ+ in photocatalytic reactions difficult to
The University of Auckland pinpoint, while also blocking attempts to exploit the unusual
Auckland 1142, New Zealand
electronic properties of Cuδ+ species to enhance photocatalytic
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201901973.
activity for reactions such as N2 fixation. Effective strategies
must be developed for the synthesis of stable semiconductor
DOI: 10.1002/aenm.201901973 photocatalysts containing low-valence Cuδ+.
Adv. Energy Mater. 2020, 10, 1901973 1901973 (1 of 10) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Previous studies have shown that the local coordina- number of photocatalytic reactions under illumination.[10,25]
tion around low-valence metal species plays a pivotal role in Doping Cu2+ (3d9) into the ZnAl-LDH layers was therefore of
determining their stability or instability.[17] For example, in interest for three reasons: 1) to see if low-valence Cuδ+ species
many photoactive Cu(I)-containing complexes (such as Cu(I) could be created and stabilized; 2) as a means of enhancing
bis(phenanthroline)-type complexes[17e] and Cu(I) bipyridine- light utilization of ZnAl-LDH photocatalysts; and 3) to
type complexes[17f ]) the ligands act cooperatively to stabilize determine whether Cuδ+ species (if formed) could enhance the
Cu(I) centers during photochemical processes.[18] The signifi- photocatalytic activity and performance of ZnAl-LDH-based
cance of the local coordination for stabilizing low-valence Cuδ+ photocatalysts in important chemical transformations, such as
species has also been demonstrated in zeolite systems, where solar-driven N2 fixation to NH3. Results of such a study were
the coordination of Cu by bridging oxygen atoms and associ- expected to be very useful to other researchers in the field
ated negative charge environment give Cuδ+ species both high attempting to engineer LDH-based photocatalysts for improved
stability and high reactivity.[19] These works serve as a useful function.
framework for the rational design of novel photocatalytic Herein, ultrathin ZnAl-LDH nanosheets containing Vo and
material with specific coordination spheres to stabilize highly low-valence Cuδ+ (i.e., electron-rich Cuδ+, where δ < 2) were
active subvalent Cuδ+. Progress in this area to date remains successfully synthesized by a facile coprecipitation strategy.
slow, prompting further investigation and the discovery of new ZnAl-LDH nanosheets doped with 0.5 mol% copper (denoted
photocatalyst design strategies. herein as 0.5%-ZnAl-LDH) exhibited outstanding and stable
Layered double hydroxides (LDHs) represent a versatile performance for photofixation of N2 to NH3 in pure water
platform for the development of new catalytic and photo- under UV–vis light irradiation at ambient temperature and
catalytic materials, owing to their controllable particle size, pressure (an NH3 evolution rate of 110 µmol g−1 h−1 was real-
compositional flexibility, and ease of synthesis.[20] LDHs are ized). Detailed structural analyses and density functional theory
laminar materials consisting of positively charged sheets of (DFT) calculations revealed that the excellent photocatalytic
edge-sharing MO6 octahedra. LDHs have the general formula performance could be attributed to the electron-rich Cuδ+ asso-
[M12−+ x M3x+ (OH)2 ]q + (A n − )q /n ⋅ mH2 O], where M2+ and M3+ are ciated with Vo in the ZnAl-LDH nanosheets (Scheme 1). The
divalent and trivalent metal cations in the positively charged existence of Vo and derivative electron-rich Cuδ+ in the ultrathin
sheets, and An− are interlayer anions such as carbonate, nitrate, ZnAl-LDH nanosheets was confirmed using a plethora of
or sulfate needed to preserve electric neutrality).[21] The exist- experimental techniques, including extended X-ray absorption
ence of OMO bridges in the LDH sheets is similar to fine structure (EXAFS), X-ray photoelectron spectroscopy
the coordination of low-valent Cuδ+ in zeolite-related com- (XPS), Auger electron spectroscopy (AES), and in situ electron
pounds,[5,22] suggesting that analogous Cuδ+ (where δ < 2) may paramagnetic resonance (EPR). The Vo and electron-rich
also be able to exist stably in LDH systems. Previous works Cuδ+ in ZnAl-LDH could facilitate separation and transfer of
have shown that coordinatively unsaturated metal species can photogenerated electrons and holes as well as the adsorption
exist in defective catalytic materials where defect vacancies, of N2 molecules, thereby delivering superior photo catalytic
such as Vo, exist adjacent to the metal centers.[9,10] Further, performance for N2 photoreduction to NH3 relative to pristine
doping Cu2+ into LDH materials offers a potential strategy for ZnAl-LDH nanosheets.
introducing Vo into LDH nanosheets through Jahn-Teller dis- Pristine ultrathin ZnAl-LDH nanosheets (denoted herein as
tortions about the Cu atom.[23] However, appropriate selection ZnAl-LDH), Cu-doped ZnAl-LDH nanosheets (denoted herein
of both the LDH host and the adding level of Cu are essential to as X-ZnAl-LDH, where X = 100% × mol Cu/mol (Zn + Al +
achieve the required coordination condition favorable for both Cu)), and CuZnAl-LDH nanosheets (Cu:Zn:Al molar ratio 1:1:1)
creating and stabilizing subvalent Cuδ+ species.[23f ] Among the were successfully prepared using a coprecipitation method (full
multitude of LDH materials that could be used for this purpose, details are provided in the Supporting Information). Figure S1
ZnAl-LDH is probably the most suitable candidate since the (Supporting Information) shows powder X-ray diffraction
atomic radius of Zn2+ (74 pm) is almost identical to that of Cu2+ (XRD) patterns for all the as-prepared LDHs nanosheets. Each
(73 pm), thereby enabling Cu(OH)6 units to be easily incorpo- sample displayed the typical (003), (006), (009), and (110) Bragg
rated into the ZnAl-LDH laminar structure during synthesis.[24] reflections associated with rhombohedral LDH structures, indi-
ZnAl-LDH photocatalysts show excellent performance in a cating that the copper dopant in the X-ZnAl-LDH samples was
Scheme 1. Strategy used for the synthesis of ZnAl-LDH nanosheets containing electron-rich Cuδ+ centers and associated Vo.
likely incorporated into the LDH rather being precipitated as (FFT) analysis (see inset of Figure 1c). The 0.5%-ZnAl-
a separate. Lattice parameters for each sample were calculated LDH nanosheets had a thickness of 4.6 nm (measured by
using the equations: a = b = 2d(110), c = 3d(003),[23a] with results atomic force microscopy (AFM), Figure 1d,e). To confirm
summarized in Figure S2 and Table S1 (Supporting Informa- the successful incorporation of Cu into the 0.5%-ZnAl-LDH
tion). Figure S2a,b (Supporting Information) shows that the nanosheets, energy-dispersive spectrometry (EDS) mapping
(110) diffraction peaks for the X-ZnAl-LDH samples shifted to was performed. Figure 1f reveals a very homogeneous distribu-
higher 2θ angles than that observed in ZnAl-LDH, indicating tion of Cu, Zn, and Al in the nanosheets. Results demonstrate
a degree of shrinkage or compressive strain was introduced that Cu was uniformly distributed into the 0.5%-ZnAl-LDH
in the host layers by copper addition. Results are consistent sample. The copper content in all the samples was quantified
with copper incorporation and the concomitant introduction of using EDS elemental analysis (Figure S4 and Table S2, Sup-
Vo.[23d] From the XRD data, we calculated the lattice parameters porting Information) and inductively coupled plasma (ICP)
and the degree of strain in all the samples,[23a] with the results spectrometry (Table S2, Supporting Information). Results are
listed in Table S1 (Supporting Information). The 0.5%-ZnAl- in good general accord with the nominal Cu contents for all
LDH sample possessed the highest in-plane compressive strain samples, confirming that the coprecipitation method used
among all the LDH samples, consistent with severe structural here to synthesize the LDH nanosheets allowed good control
distortions imposed by an abundance of Vo. A high prevalence of the Cu content in the final products (and by analogy a way
of Vo in the 0.5%-ZnAl-LDH sample, and therefore the pos- of optimizing the amount of Vo and electron-rich Cuδ+ in the
sibility of copper in a CuO5(Vo) coordination rather than the final products).
CuO6 coordination expected in LDH materials, would offer the To explore the local atomic coordination of zinc and copper
ideal coordination condition for the formation of electron-rich in the various LDH samples, X-ray absorption spectra (XAS)
Cuδ+ centers. As stated above, Vo and electron-rich Cuδ+ were were collected (Figure 2, Figures S5a–c and S6a–c, Supporting
hypothesized to provide excellent active sites for N2 fixation to Information). First, the local coordination state of Zn in ZnAl-
NH3, as was confirmed through detailed experiments described LDH, X-ZnAl-LDH (X = 0.25, 0.5, 1, 3 mol%) and CuZnAl-
next. LDH will be explored. Figure S5a,b (Supporting Information)
Transmission electron microscopy (TEM) images for all shows X-ray absorption near-edge fine structure (XANES) and
the as-synthesized LDHs nanosheets show the expected EXAFS k-space spectra for zinc ions in these samples. Data for
platelet morphology (Figure 1a,b and Figure S3, Supporting all samples were reasonably similar at a quick glance, and con-
Information). The high-resolution TEM (HRTEM) image of sistent with the presence of Zn2+ ions. The presence of Zn2+ in
0.5%-ZnAl-LDH displays a lattice fringe spacing of 0.26 nm all the samples was also verified by XPS analyses (Figure S5d,
(Figure 1c), which can be assigned to the (012) crystal plane of Supporting Information). The EXAFS R-space data provided
the LDH structure,[10] as is verified by a fast Fourier transform detailed information about the ZnO coordination shell in the
Figure 1. a,b) TEM images at different magnifications of 0.5%-ZnAl-LDH nanosheets. c) HRTEM image of 0.5%-ZnAl-LDH nanosheets (the inset
shows the FFT analysis). d,e) AFM image and the corresponding height profiles for 0.5%-ZnAl-LDH nanosheets (the numbers 1, 2, and 3 correspond
to the line scan numbers in (d)). f) EDS element maps for 0.5%-ZnAl-LDH.
Figure 2. a) Cu K-edge XANES spectra. b) Cu K-edge EXAFS oscillation functions k2χ(k). c) Magnitude of k2-weighted FT of Cu K-edge EXAFS spectra
for 0.5%-ZnAl-LDH and CuZnAl-LDH. d) Cu 2p XPS spectra for 0.5%-ZnAl-LDH and CuZnAl-LDH. e) Schematic showing the simultaneous evolution
of electron-rich Cuδ+ and Vo.
LDHs (Figure S5c, Supporting Information). Compared with range 0–10 Å (Figure 2b), suggesting subtle variations in the
ZnAl-LDH, the Zn K-edge R-space plots for the X-ZnAl-LDHs local environments around the Cu atoms in these two sam-
had weaker intensity ZnO peaks, implying a degree of coordi- ples, which was clearly evident in the corresponding R-space
native unsaturation existed about zinc atoms in these samples. plots (Figure 2c). The EXAFS R-space spectra for the two
It is noteworthy that 0.5%-ZnAl-LDH possessed the highest samples showed two peaks, corresponding to the first CuO
degree of unsaturation about the Zn atoms among the different shell and Cu–metal shell. Compared with CuZnAl-LDH (an
samples, suggesting a higher abundance of Vo. Interestingly, average CuO distance of 1.93 Å and a coordination number
0.5%-ZnAl-LDH and CuZnAl-LDH had a similar degree of of 6.0 for the first CuO coordination sphere), the 0.5%-ZnAl-
coordinative unsaturation about Zn (Figure S5c, Supporting LDH samples showed a longer CuO distance (1.99 Å) and a
Information). Subsequently, we explored the local coordina- lower coordination number (5.38). This provides convincing
tion of copper ions in the different samples, with the results evidence that Cu in 0.5%-ZnAl-LDH possessed a high degree
presented in Figure 2a–c and Figure S6a–c (Supporting Infor- of coordinative unsaturation, and abundant Vo leading to
mation). By careful analysis of the Cu K-edge XANES spectra structural distortions and strain within the LDH nanosheets
(Figure 2a), it is evident that Cu K-edge peak maximum for (Table S3, Supporting Information). The Debye–Waller factor
the 0.5%-ZnAl-LDH sample (8996.35 eV) was 0.52 eV lower of the CuO shell (5.42 Å2) for 0.5%-ZnAl-LDH was much
than that for the CuZnAl-LDH sample (8996.87 eV), consistent larger than that determined for CuZnAl-LDH (3.63 Å2), further
with a lower average oxidation state of copper (i.e., Cuδ+, δ < 2) evidence for severe structural distortion in the 0.5%-ZnAl-LDH
in 0.5%-ZnAl-LDH.[3] Further, 0.5%-ZnAl-LDH and CuZnAl- sample. Taken collectively, these results suggest the formation
LDH differed noticeably in their Cu K-edge oscillations in the of Vo around Cu centers in 0.5%-ZnAl-LDH, thus providing
favorable conditions for the existence of electron-rich Cuδ+ in For 0.5%-ZnAl-LDH, the Auger signal was broader and less
the sample (as depicted schematically in Figure 2e). well-defined compared to that collected for CuZnAl-LDH,
To further ascertain the existence of electron-rich Cuδ+ in suggesting the presence of Cu in several valence states in the
0.5%-ZnAl-LDH, we performed XPS and AES analyses on 0.5%-ZnAl-LDH sample (i.e., Cu+ and Cu2+).[27] The XPS and
the sample (Figure 2d and Figure S6d, Supporting Informa- AES results thus provided strong evidence for the presence of
tion). The Cu 2p XPS spectrum for 0.5%-ZnAl-LDH showed electron-rich Cuδ+ in the 0.5%-ZnAl-LDH, which is consistent
signals due to Cu+ (peaks at 932.9 and 952.4 eV for 2p3/2 and with the XAS findings.
2p1/2, respectively) and Cu2+ (peaks at 934.7 and 954.7 eV for To explore the role of Vo and electron-rich Cuδ+ in promoting
2p3/2 and 2p1/2, respectively), indicating that the sample was photocatalytic reactions, we evaluated the performance of
indeed low valent (i.e., contained Cuδ+, δ < 2). In comparison, X-ZnAl-LDH and the various reference photocatalysts (ZnAl-
the CuZnAl-LDH sample only contained Cu2+ ions.[26] X-ray- LDH and CuZnAl-LDH) for photocatalytic nitrogen fixation
excited LMM Auger spectra were also collected for 0.5%-ZnAl- under UV–vis irradiation (Figure 3a). The photocatalytic activity
LDH and CuZnAl-LDH to further probe the valence of Cu of all samples was assessed in N2-saturated water under UV–
in these samples (Figure S6d, Supporting Information). vis (Xe lamp) irradiation at ambient temperature and pressure,
Figure 3. a) Schematic depiction of photocatalytic N2 fixation on the surface of ZnAl-LDH nanosheets with Vo and electron-rich Cuδ+. b) Photocatalytic
ammonia production rates for ZnAl-LDH, 0.25%-ZnAl-LDH, 0.5%-ZnAl-LDH, 1%-ZnAl-LDH, 3%-ZnAl-LDH, and CuZnAl-LDH in N2-saturated water
under UV–vis irradiation. c) Time-dependent photocatalytic N2 reduction and control experiments by 0.5%-ZnAl-LDH over 40 h. d) Photocatalytic
stability cycle tests for 0.5%-ZnAl-LDH in N2-saturated water under UV–vis irradiation. e) Mass spectra of the indophenol products obtained by reaction
of photocatalytically generated ammonia with phenol. The experiments used 14N2 or 15N2 (the inset shows the chemical structure of the indophenol
product responsible for the signals at m/z 198 (containing 14N) and 199 (containing 15N). f) In situ DRIFTS spectra collected from 0.5%-ZnAl-LDH
during photocatalytic N2 fixation.
using ion chromatography for accurate ammonia quanti- washing before illumination (Figure S16g,h, Supporting Infor-
fication.[28] As shown in Figure 3b, all the LDH samples mation), photoreaction using argon (Ar) instead of N2 and dark
were active for photocatalytic N2 fixation, with the rates of reaction in which the amounts of ammonia were much lower
ammonia production following the order: 0.5%-ZnAl-LDH than that detected in N2 photoreduction reaction (Figure 3c and
(110 µmol g−1 h−1) > 1%-ZnAl-LDH (50 µmol g−1 h−1) > Figure S17, Supporting Information).
0.25%-ZnAl-LDH (42.6 µmol g−1 h−1) > 3%-ZnAl-LDH To further confirm that photocatalytic N2 fixation reaction
(37.6 µmol g−1 h−1) > CuZnAl-LDH (31.1 µmol g−1 h−1) > ZnAl- occurred on the surface of 0.5%-ZnAl-LDH, in situ diffuse
LDH (17.1 µmol g−1 h−1). These results hint at the key role of reflectance infrared Fourier transformation spectroscopy
Vo and Cuδ+ in promoting photocatalytic N2 fixation.[2] To account (DRIFTS) was applied to monitor the surface intermediates
for differences in the specific surface area between the photo- formed during photocatalytic N2 fixation (Figure 3f). During
catalysts, we divided the NH3 production rates (in µmol g−1 h−1) the photoreaction (i.e., under light irradiation) over 0.5%-ZnAl-
by the corresponding Brunauer–Emmett–Teller (BET) specific LDH, various signals intensified with reaction time. Peaks at
surface area (in m2 g−1) of each sample, thus obtaining area 3555 and 3246 cm−1 can readily be assigned to asymmetric
normalized NH3 production rates (in µmol m−2 h−1) (Figures ν(NH) stretching modes of NH3.[29] Similarly, peaks at 1740
S7 and S8, Supporting Information). The similar trend was and 1460 cm−1 are σ(HNH) bending vibration of NH3.[30]
found, with the 0.5%-ZnAl-LDH photocatalyst affording a The signal at 1648 cm−1 corresponds to an antisymmetric
much higher ammonia production rate (4.12 µmol m−2 h−1) deformation vibration of NH4+.[23a] The intensification of these
relative to the other samples. Clearly, the abundance of Vo signals as the reaction proceeded provides evidence that NH3
and electron-rich Cuδ+ sites in 0.5%-ZnAl-LDH enhanced its was continually being formed on the surface of the 0.5%-ZnAl-
photocatalytic performance for N2 fixation. We further perform LDH photocatalyst. Additional bands at 1692 and 1268 cm−1 are
time-dependent photocatalytic N2 fixation experiment with associated with bending modes of NH and NH2 species,
continuous light irradiation more than 40 h over 0.5%-ZnAl- respectively.[30a,31] The observation of NH3 and various other
LDH alongside rigorous control experiments (Figure 3c). The reaction intermediates implies that the 0.5%-ZnAl-LDH photo-
amount of produced ammonia is increased linearly as the reac- catalyst was very effective for activating NN bonds in the pres-
tion time increased with intuitive ion chromatography data ence of H2O under UV–vis illumination.
for NH4+ presented in Figure S9 (Supporting Information). To evaluate the light utilization efficiency, the wavelength-
Although the reaction rate did not remain constant during dependent quantum efficiency (QE) of 0.5%-ZnAl-LDH was
40 h irradiation, which may be affected by the consumption, determined by measuring the amount of ammonia produced
dissolution, and adsorption of N2, the amount of produced under monochromatic light irradiation (wavelengths 265, 365,
ammonia is still gradually increased by prolonging photoreac- 400, or 420 nm) (Figure S18a, Supporting Information). Spe-
tion time, corroborating the outstanding durability of our LDH cifically, monochromatic light of wavelengths 265 and 365 nm
nanosheets containing Vo and electron-rich Cuδ+. afforded N2 photoreduction performance with the QE of 1.77%
In addition, the 0.5%-ZnAl-LDH photocatalyst showed no and 0.56%, respectively. However, 0.5%-ZnAl-LDH demon-
obvious decrease in NH3 production activity over successive strated almost no photocatalytic activity for N2 reduction under
eight photocatalytic cycles (Figure 3d) and also no significant monochromatic light of wavelengths 400 and 420 nm. To
change in morphology, phase structure or chemical composi- objectively assess the photocatalytic performance for practical
tion of photocatalyst (Figures S10–S12, Supporting Information). applications, we further determine the light-to-chemical conver-
Results indicate that 0.5%-ZnAl-LDH displayed outstanding sion (LCC) efficiency of 0.5%-ZnAl-LDH in N2-saturated water
photocatalytic stability under the conditions of the N2 fixation under xenon lamp and simulated AM 1.5G sunlight irradiation.
experiments. As shown in Figures S13 and S14 (Supporting As a consequence, the calculated LCC efficiencies were 0.0042%
Information), neither N2H4 nor NO3− were detected during for xenon lamp irradiation and 0.014% for AM 1.5G irradiation.
the photocatalytic tests, only very small amount of hydrogen To gain deeper insights about the role of electron-rich Cuδ+
produced from water could be detected by gas chromatog- in promoting photocatalytic N2 fixation, we carried out in
raphy (Figure S15, Supporting Information), indicating situ EPR experiments under a constant N2 flow, as depicted
that 0.5%-ZnAl-LDH offered excellent selectivity (≈92%) for in Figure 4a. According to the operating principles of EPR,
reduction of N2 to NH3. unpaired free electrons in the atomic orbitals or molecular
To confirm that the NH3 detected in this study was generated orbitals will be excited to higher energy levels under and
by direct N2 photofixation, as opposed to arising from other applied external magnetic field, thus generating a character-
sources, isotope labeling experiments using 15N2 and various istic EPR signal (Figure 4b).[32] Before photoirradiation, the
control experiments were performed. When 15N2 was used as 0.5%-ZnAl-LDH sample showed the conspicuous signature of
the feed gas, the products of 15NH4+ can be detected using the Cu2+ (3d9), (Cu+ (3d10) in the sample would not be detected by
indophenol blue method[28] coupled with high-resolution mass EPR).[33] In many semiconductor systems, free electrons are
spectroscopy (Figure 3e). The obtained indophenol products typically located on sites around Vo, as has been reported for
containing 15N and 14N gave characteristic mass spectrometry TiO2-Vo,[2] CuCr-LDH,[23a] and BiOBr-Vo.[29a,b] Accordingly, the
signals at m/z 199 and m/z 198, respectively. These results presence of Vo may have acted to enrich the number of free
confirm that the NH3 detected in this work originated from N2 electrons on the Cu centers in 0.5%-ZnAl-LDH, probably giving
photofixation, which was further verified by a series of rigorous the sample a very intense EPR signal. In comparison, CuZnAl-
control experiments, including photocatalysts composition anal- LDH containing much more copper (as Cu2+) gave a weaker
ysis (Figure S16a–f, Supporting Information), photocatalysts and broader EPR signal, which is attributed to the formation
Figure 4. a) Schematic showing the in situ EPR experiment. b) Octahedral crystal field diagram showing the unpaired d electron responsible for the
observation of the EPR signal. c) EPR spectra for ZnAl-LDH, 0.5%-ZnAl-LDH, and CuZnAl-LDH in the dark. d) In situ EPR for 0.5%-ZnAl-LDH measured
in the dark and after 20 min light irradiation. e) Side view of the charge density distribution of the 0.5%-ZnAl-LDH surface. The isosurface value is
0.001 e Å−3. Yellow and blue contour regions indicate zones of electron accumulation and depletion, respectively.
of EPR silent species (e.g., Cu2+ ion dimers) or dipolar interac- in 0.5%-ZnAl-LDH. In addition, electronegativity differences
tions between Cu2+ ions, significantly lowering the availability between the coordinated metal atoms (Cu (1.90) > Zn (1.65)
of free electrons.[34] Further, we studied the intensity of the Cu2+ > Al (1.61))[36] would favor the formation of electron-rich Cuδ+
EPR signal for the 0.5%-ZnAl-LDH under UV–vis illumination in the X-ZnAl-LDHs. On the basis of this information, the
(Figure 4d) to see if photogenerated electrons were transferred superior photocatalytic performance of 0.5%-ZnAl-LDH for N2
to the Cu centers under light irradiation (thus reducing some reduction to NH3 can be understood. The sample contains an
Cu2+ to low-valence Cuδ+).[35] The Cu2+ EPR signal lost inten- abundance of Vo and nearby electron-rich Cuδ+, thus allowing
sity under UV–vis irradiation for 20 min, quantifiable evidence the N2 to adsorb on the surface of LDH nanosheets where
for the reduction of some Cu2+ to lower valence Cu states. the transfer of electrons to the N2 molecule can readily occur
Theoretically, this is explored in Figure 4e, where an obvious (with electrons arriving at the Vo with adjacent Cuδ+ centers via
charge density difference is observed between the Cu center photoexcitation processes in the LDH nanosheets).[29a,b]
(electron depletion region, colored blue) and the surrounding For any photocatalyst, the optical absorption characteristics
Vo (electron accumulation region, colored yellow). The coor- are important. UV–vis diffuse reflectance spectra (UV-DRS)
dinatively unsaturated Cu atom carriers a less positive Bader for all the LDHs samples prepared in this study are shown in
charge (0.16 e) than the corresponding Cu atom (0.21 e) in Figure S19 (Supporting Information). As the content of Cu
the pristine sample, further evidence for electron-rich Cuδ+ dopants increased, the absorption band in the 200–400 nm
intensified (this feature is associated with electronic transitions porting Information), in which an obvious enhancement of the
from O 2p orbitals to Cu 3d and Zn 3d orbitals).[35a] The Cu d-d current density was found in N2-saturated solutions than that
transition near 800 nm also intensified with the Cu addition,[11b] in Ar-saturated solutions. All of these attributes are expected to
further evidence for the successful incorporation of Cu into the be highly beneficial for enhancing ammonia synthesis, hence
ZnAl-LDH nanosheets (consistent with EDS and ICP results the superior performance of 0.5%-ZnAl-LDH for dinitrogen
discussed above). As noted above, no obvious relationship fixation relative to the other LDH materials tested in this study.
could be established between the photocatalytic performance DFT calculations were employed to investigate the N2 adsorp-
of as-prepared LDH samples and light absorption, indicating tion capacity of the photocatalysts. Crystal models were con-
that the enhanced light absorption properties achieved through structed for pristine ZnAl-LDH, ZnAl-LDH with oxygen vacan-
Cu doping had minor influence on the photocatalytic perfor- cies (denoted as ZnAl-LDH-Vo), and ZnAl-LDH containing Vo
mance of these particular LDH photocatalysts. Instead, the and electron-rich Cuδ+ (denoted as Cu-doped ZnAl-LDH-Vo).
presence of an abundance of Vo and electron-rich Cuδ+ is the The adsorption of N2 molecules on catalytic sites is usually
key for enhancing photocatalytic ammonia synthesis. Further- regarded as the important decisive step for N2 fixation,[37] which
more, Mott–Schottky (M–S) and Tauc analyses were collected can be gauged from the adsorption energy of an adsorbed N2
to evaluate energy band structure for ZnAl-LDH, 0.5%-ZnAl- molecule on the surface of catalysts (Figures S23 and S24, Sup-
LDH, and CuZnAl-LDH. The flat band potential of 0.5%-ZnAl- porting Information).[29a] The adsorption energies for adsorbed
LDH was calculated to be −0.27 V (vs the normal hydrogen N2 on pristine-ZnAl-LDH, ZnAl-LDH-Vo, and Cu-doped ZnAl-
electrode, NHE), which is more negative than that determined LDH-Vo were −0.03, −0.54, and −0.94 eV, respectively. The cal-
for ZnAl-LDH (−0.21 V vs NHE) and CuZnAl-LDH (−0.18 V culated results suggest that Vo and Cu-doping was effective in
vs NHE) (Figure S18b, Supporting Information). Judging by promoting N2 adsorption and thus providing a prerequisite for
the UV-DRS measurements (Figure S18c, Supporting Infor- weakening the interatomic N2 triple bond, hence facilitating the
mation), the bandgap for 0.5%-ZnAl-LDH was estimated to be N2 reduction to NH3.
≈3.95 eV. Accordingly, N2 photoreduction to NH3 is thermody- In summary, ultrathin ZnAl-LDH nanosheets containing
namically achievable over 0.5%-ZnAl-LDH containing Vo and Vo and electron-rich Cuδ+ were successfully synthesized by
electron-rich Cuδ+ (N2/NH3 reduction potential ≈ 0.055 V vs facile coprecipitation method. 0.5%-ZnAl-LDH nanosheets
NHE) (Figure S18d, Supporting Information). Besides, it is (0.5 mol% Cu doping) possess an abundance of Vo and
well-known that Vo plays a key role in decreasing NRR reaction coordinatively unsaturated Cuδ+ with electron-rich property
barriers, thus offering a lower energy pathway for the conver- and exhibited excellent photocatalytic activity and stability
sion of N2 to NH3 over the 0.5%-ZnAl-LDH photocatalyst. for N2 reduction to NH3 in water under UV–vis irradiation.
Since N2 reduction to NH3 requires multielectron transfer A rate of 110 µmol g−1 h−1 (4.12 µmol m−2 h−1) was realized
(i.e., N2 + 6H+ + 6e− → 2NH3), the efficiency of the LDH at atmospheric pressure and temperature in the absence of
nanosheets to transfer electrons plays an imperative role in any sacrificial agent or added cocatalyst. The Vo and electron-
boosting N2 photoreduction process. We first investigated the rich Cuδ+ in 0.5%-ZnAl-LDH were efficient in promoting N2
charge transfer resistance by electrochemical impedance spec- molecules adsorption and charge separation/transfer, thereby
troscopy (EIS), with and without illumination. As shown in efficient N2 reduction. The synthetic strategy to synthesize
Figure S20a (Supporting Information), the diameter of the ZnAl-LDH abundant in Vo and electron-rich Cuδ+ could easily
semicircle Nyquist plot for 0.5%-ZnAl-LDH was smaller than be adapted to synthesize other LDH materials containing
that of ZnAl-LDH, indicating a lower charge-transfer resist- highly active metal sites, thus offering a simple and low-cost
ance and more efficient electron transfer in 0.5%-ZnAl-LDH. pathway to an inventory of new and efficient photocatalytic
Further, both 0.5%-ZnAl-LDH and ZnAl-LDH demonstrated materials for N2 photoreduction and other important chemical
smaller semicircles under light irradiation, suggesting that transformations.
enhanced electron transfer was realized by photoexcitation of
these materials. Moreover, photocurrent and time-resolved
photoluminescence decay measurements were carried out to Supporting Information
investigate photoinduced charge separation/transfer in as-pre-
pared LDH nanosheets. The data in Figure S21 (Supporting Supporting Information is available from the Wiley Online Library or
from the author.
Information) indicate that 0.5%-ZnAl-LDH displayed much
larger photocurrent density than its counterparts, suggesting
enhanced electron and hole separation/transfer in 0.5%-ZnAl-
LDH. Furthermore, time-resolved photoluminescence curves Acknowledgements
(Figure S22, Supporting Information) revealed that the S.Z. and Y.Z. contributed equally to this work. The authors are
0.5%-ZnAl-LDH nanosheets had longer average decay times grateful for financial support from the National Key Projects for
(≈3.34 ns) compared with that obtained in ZnAl-LDH (≈1.85 Fundamental Research and Development of China (2018YFB1502002,
ns), which provides solid evidence that the Vo and electron-rich 2017YFA0206904, 2017YFA0206900, 2016YFB0600901), the National
Cuδ+ in 0.5%-ZnAl-LDH serve to promote the separation of Natural Science Foundation of China (51825205, 51772305, 51572270,
U1662118, 21871279, 21802154, 21902168), the Beijing Natural Science
photogenerated electrons and holes (by accepting electrons) and Foundation (2191002, 2182078, 2194089), the Strategic Priority Research
would transfer those electrons to the surface of LDH nanosheets Program of the Chinese Academy of Sciences (XDB17000000), the Royal
for better N2 adsorption and activation, which could be further Society Newton Advanced Fellowship (NA170422), the International
verified by linear sweep voltammetry (LSV) (Figure S20b, Sup- Partnership Program of Chinese Academy of Sciences (GJHZ1819,
GJHZ201974), the Beijing Municipal Science and Technology Project [11] a) X. Sun, J. Lin, J. Phys. Chem. C 2009, 113, 4970; b) W. Y. Lin,
(Z181100005118007), and the K. C. Wong Education Foundation and H. Frei, J. Am. Chem. Soc. 2005, 127, 1610; c) T.-H. Xie, X. Sun,
the Youth Innovation Promotion Association of the CAS. The XAFS J. Lin, J. Phys. Chem. C 2008, 112, 9753; d) R. Nakamura,
experiments were conducted in 1W1B beamline of Beijing Synchrotron A. Okamoto, H. Osawa, H. Irie, K. Hashimoto, J. Am. Chem. Soc.
Radiation Facility (BSRF). The authors thank the BioNMR facility, 2007, 129, 9596.
Tsinghua University Branch of China National Center for Protein [12] a) M. Hara, T. Kondo, M. Komoda, S. Ikeda, K. Shinohara,
Sciences (Beijing). G.I.N.W. acknowledges funding support from Greg A. Tanaka, J. N. Kondo, K. Domen, Chem. Commun. 1998, 357;
and Kathryn Trounson (via a generous philanthropic donation), the b) H. Jiang, K.-I. Katsumata, J. Hong, A. Yamaguchi, K. Nakata,
Energy Education Trust of New Zealand, and the MacDiarmid Institute
C. Terashima, N. Matsushita, M. Miyauchi, A. Fujishima, Appl.
for Advanced Materials and Nanotechnology.
Catal., B 2018, 224, 783; c) G. Centi, S. Perathoner, Appl. Catal., A
1995, 132, 179.
[13] J. Luo, L. Steier, M.-K. Son, M. Schreier, M. T. Mayer, M. Graetzel,
Conflict of Interest Nano Lett. 2016, 16, 1848.
[14] S. Paria, O. Reiser, ChemCatChem 2014, 6, 2477.
The authors declare no conflict of interest. [15] L. Liu, C. Zhao, Y. Li, J. Phys. Chem. C 2012, 116, 7904.
[16] C. Wang, B. Ma, S. Xu, D. Li, S. He, Y. Zhao, J. Han, M. Wei,
D. G. Evans, X. Duan, Nano Energy 2017, 32, 463.
[17] a) C. van der Linde, S. Hemmann, R. F. Hoeckendorf, O. P. Balaj,
Keywords M. K. Beyer, J. Phys. Chem. A 2013, 117, 1011; b) Y. Z. Wang,
electron-rich Cuδ+, nitrogen fixation, oxygen vacancies, photocatalysis, B. Quillian, P. R. Wei, H. Y. Wang, X. J. Yang, Y. M. Xie, R. B. King,
ultrathin LDH nanosheets P. V. Schleyer, H. F. Schaefer, G. H. Robinson, J. Am. Chem. Soc.
2005, 127, 11944; c) T. Li, S. Schulz, P. W. Roesky, Chem. Soc.
Received: June 19, 2019 Rev. 2012, 41, 3759; d) J. Wang, L. Y. Gan, Q. W. Zhang, V. Reddu,
Revised: December 17, 2019 Y. C. Peng, Z. C. Liu, X. H. Xia, C. Wang, X. Wang, Adv. Energy
Published online: January 15, 2020 Mater. 2019, 9, 1803151; e) N. Armaroli, Chem. Soc. Rev. 2001,
30, 113; f) Y.-J. Yuan, Z.-T. Yu, J.-Y. Zhang, Z.-G. Zou, Dalton Trans.
2012, 41, 9594.
[18] a) R. S. Khnayzer, C. E. McCusker, B. S. Olaiya, F. N. Castellano,
[1] a) C. Guo, J. Ran, A. Vasileff, S.-Z. Qiao, Energy Environ. Sci. 2018, J. Am. Chem. Soc. 2013, 135, 14068; b) E. Mejia, S.-P. Luo,
11, 45; b) S. Zhang, Y. Zhao, R. Shi, G. I. N. Waterhouse, T. Zhang, M. Karnahl, A. Friedrich, S. Tschierlei, A.-E. Surkus, H. Junge,
EnergyChem 2019, 1, 100013; c) X. liu, Y. Jiao, Y. Zheng, M. Jaroniec, S. Gladiali, S. Lochbrunner, M. Beller, Chem. - Eur. J. 2013, 19,
S.-Z. Qiao, J. Am. Chem. Soc. 2019, 141, 9664; d) X. Chen, N. Li, 15972; c) S. P. Luo, E. Mejia, A. Friedrich, A. Pazidis, H. Junge,
Z. Kong, W.-J. Ong, X. Zhao, Mater. Horiz. 2018, 5, 9. A. E. Surkus, R. Jackstell, S. Denurra, S. Gladiali, S. Lochbrunner,
[2] H. Hirakawa, M. Hashimoto, Y. Shiraishi, T. Hirai, J. Am. Chem. M. Beller, Angew. Chem., Int. Ed. 2013, 52, 419; d) N. Armaroli,
Soc. 2017, 139, 10929. G. Accorsi, M. Holler, O. Moudam, J.-F. Nierengarten, Z. Zhou,
[3] Y. Zhao, C. Chang, F. Teng, Y. Zhao, G. Chen, R. Shi, R. T. Wegh, R. Welter, Adv. Mater. 2006, 18, 1313.
G. I. N. Waterhouse, W. Huang, T. Zhang, Adv. Energy Mater. 2017, [19] a) R. Bulanek, B. Wichterlova, Z. Sobalik, J. Tichy, Appl. Catal., B
7, 1700005. 2001, 31, 13; b) A. Zecchina, S. Bordiga, G. T. Palomino, D. Scarano,
[4] H. B. Yang, S.-F. Hung, S. Liu, K. Yuan, S. Miao, L. Zhang, C. Lamberti, M. Salvalaggio, J. Phys. Chem. B 1999, 103, 3833.
X. Huang, H.-Y. Wang, W. Cai, R. Chen, J. Gao, X. Yang, W. Chen, [20] a) Y. Zhao, X. Jia, G. I. N. Waterhouse, L.-Z. Wu, C.-H. Tung,
Y. Huang, H. M. Chen, C. M. Li, T. Zhang, B. Liu, Nat. Energy 2018, D. O’Hare, T. Zhang, Adv. Energy Mater. 2016, 6, 1501974;
3, 140. b) Z. Wang, S.-M. Xu, Y. Xu, L. Tan, X. Wang, Y. Zhao, H. Duan,
[5] G. Chen, Y. Zhao, L. Shang, G. I. N. Waterhouse, X. Kang, L.-Z. Wu, Y.-F. Song, Chem. Sci. 2019, 10, 378; c) J. Zhang, J. Liu, L. Xi, Y. Yu,
C.-H. Tung, T. Zhang, Adv. Sci. 2016, 3, 1500424. N. Chen, S. Sun, W. Wang, K. M. Lange, B. Zhang, J. Am. Chem.
[6] X. Du, J. Huang, J. Zhang, Y. Yan, C. Wu, Y. Hu, C. Yan, T. Lei, Soc. 2018, 140, 3876; d) D. Zhou, S. Wang, Y. Jia, X. Xiong, H. Yang,
W. Chen, C. Fan, J. Xiong, Angew. Chem., Int. Ed. 2019, 58, 4484. S. Liu, J. Tang, J. Zhang, D. Liu, L. Zheng, Y. Kuang, X. Sun, B. Liu,
[7] a) D. Walther, E. Dinjus, J. Sieler, L. Andersen, O. Lindqvist, Angew. Chem., Int. Ed. 2019, 58, 736.
J. Organomet. Chem. 1984, 276, 99; b) T. Bollermann, [21] Q. Wang, D. O’Hare, Chem. Rev. 2012, 112, 4124.
G. Prabusankar, C. Gemel, R. W. Seidel, M. Winter, R. A. Fischer, [22] a) Z. Cai, D. Zhou, M. Wang, S. M. Bak, Y. Wu, Z. Wu, Y. Tian,
Chem. - Eur. J. 2010, 16, 8846; c) A. F. Hill, W. R. Roper, X. Xiong, Y. Li, W. Liu, S. Siahrostami, Y. Kuang, X. Q. Yang,
J. M. Waters, A. H. Wright, J. Am. Chem. Soc. 1983, 105, 5939; H. Duan, Z. Feng, H. Wang, X. Sun, Angew. Chem., Int. Ed. 2018,
d) D. Gallego, S. Inoue, B. Blom, M. Driess, Organometallics 2014, 33, 57, 9392; b) Y. Zhao, Q. Wang, T. Bian, H. Yu, H. Fan, C. Zhou,
6885. L.-Z. Wu, C.-H. Tung, D. O’Hare, T. Zhang, Nanoscale 2015, 7,
[8] a) A. Sagadevan, K. C. Hwang, Adv. Synth. Catal. 2012, 354, 3421; 7168.
b) P. A. Grutsch, C. Kutal, J. Am. Chem. Soc. 1979, 101, 4228; [23] a) Y. Zhao, Y. Zhao, G. I. N. Waterhouse, L. Zheng, X. Cao, F. Teng,
c) D. T. Ziegler, J. Choi, J. M. Munoz-Molina, A. C. Bissember, L. Z. Wu, C. H. Tung, D. O’Hare, T. Zhang, Adv. Mater. 2017,
J. C. Peters, G. C. Fu, J. Am. Chem. Soc. 2013, 135, 13107; 29, 1703828; b) R. D. Shannon, Acta Crystallogr., Sect. A: Found.
d) D. Hien-Quang, S. Bachman, A. C. Bissember, J. C. Peters, Crystallogr. 1976, 32, 751; c) X. Pan, M.-Q. Yang, X. Fu, N. Zhang,
G. C. Fu, J. Am. Chem. Soc. 2014, 136, 2162. Y.-J. Xu, Nanoscale 2013, 5, 3601; d) Q. Wu, Q. Zheng, R. van
[9] a) Y. Zhao, B. Li, Q. Wang, W. Gao, C. J. Wang, M. Wei, D. G. Evans, de Krol, J. Phys. Chem. C 2012, 116, 7219; e) Y. Zhao, Y. Zhao, R. Shi,
X. Duan, D. O’Hare, Chem. Sci. 2014, 5, 951; b) X. Chen, X. Zhao, B. Wang, G. I. N. Waterhouse, L. Z. Wu, C. H. Tung, T. Zhang, Adv.
Z. Kong, W.-J. Ong, N. Li, J. Mater. Chem. A 2018, 6, 21941. Mater. 2019, 31, 1806482; f) G. Fan, F. Li, D. G. Evans, X. Duan,
[10] Y. Zhao, G. Chen, T. Bian, C. Zhou, G. I. Waterhouse, L. Z. Wu, Chem. Soc. Rev. 2014, 43, 7040.
C. H. Tung, L. J. Smith, D. O’Hare, T. Zhang, Adv. Mater. 2015, 27, [24] Y.-H. Lu, W.-H. Lin, C.-Y. Yang, Y.-H. Chiu, Y.-C. Pu, M.-H. Lee,
7824. Y.-C. Tseng, Y.-J. Hsu, Nanoscale 2014, 6, 8796.
[25] a) H. Wang, X. Xiang, F. Li, AlChE J. 2010, 56, 768; Chem. Soc. 2018, 140, 9434; b) J. Yang, Y. Guo, R. Jiang, F. Qin,
b) F. Rodriguez-Rivas, A. Pastor, C. Barriga, M. Cruz-Yusta, H. Zhang, W. Lu, J. Wang, J. C. Yu, J. Am. Chem. Soc. 2018, 140,
L. Sanchez, I. Pavlovic, Chem. Eng. J. 2018, 346, 151. 8497.
[26] a) P. Liu, E. J. M. Hensen, J. Am. Chem. Soc. 2013, 135, 14032; [31] P. C. Huang, W. Liu, Z. H. He, C. Xiao, T. Yao, Y. M. Zou,
b) I. Platzman, R. Brener, H. Haick, R. Tannenbaum, J. Phys. Chem. C. M. Wang, Z. M. Qi, W. Tong, B. C. Pan, S. Q. Wei, Y. Xie, Sci.
C 2008, 112, 1101. China Chem. 2018, 61, 1187.
[27] J. Sun, J. Yu, Q. Ma, F. Meng, X. Wei, Y. Sun, N. Tsubaki, Sci. Adv. [32] W. J. Rink, Radiat. Meas. 1997, 27, 975.
2018, 4, eaau3275. [33] S. Docao, A. R. Koirala, M. G. Kim, I. C. Hwang, M. K. Song,
[28] Y. Zhao, R. Shi, X. Bian, C. Zhou, Y. Zhao, S. Zhang, F. Wu, K. B. Yoon, Energy Environ. Sci. 2017, 10, 628.
G. I. N. Waterhouse, L. Z. Wu, C. H. Tung, T. Zhang, Adv. Sci. 2019, [34] F. Gao, E. D. Walter, M. Kollar, Y. Wang, J. Szanyi, C. H. F. Peden,
6, 1802109. J. Catal. 2014, 319, 1.
[29] a) H. Li, J. Shang, Z. Ai, L. Zhang, J. Am. Chem. Soc. 2015, 137, [35] a) N. Baliarsingh, L. Mohapatra, K. Parida, J. Mater. Chem. A 2013,
6393; b) X. Xue, R. Chen, H. Chen, Y. Hu, Q. Ding, Z. Liu, L. Ma, 1, 4236; b) Y. Kuroda, Y. Yoshikawa, S.-i. Konno, H. Hamano,
G. Zhu, W. Zhang, Q. Yu, J. Liu, J. Ma, Z. Jin, Nano Lett. 2018, 18, H. Maeda, R. Kumashiro, M. Nagao, J. Phys. Chem. 1995, 99,
7372; c) H. Yuzawa, T. Mori, H. Itoh, H. Yoshida, J. Phys. Chem. C 10621.
2012, 116, 4126. [36] S. S. Batsanov, Inorg. Mater. 2001, 37, 23.
[30] a) N. Zhang, A. Jalil, D. Wu, S. Chen, Y. Liu, C. Gao, W. Ye, [37] L. M. Azofra, N. Li, D. R. MacFarlane, C. Sun, Energy Environ. Sci.
Z. Qi, H. Ju, C. Wang, X. Wu, L. Song, J. Zhu, Y. Xiong, J. Am. 2016, 9, 2545.

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Efficient Photocatalytic Nitrogen Fixation over Cuδ+-

new strategies for enhancing N2 adsorp-

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