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Article
Mechanism of Photocatalytic CO Reduction by Bismuth-
2
Based Perovskite Nanocrystals at the Gas-Solid Interface

Sumit S. Bhosale, Aparna K. Kharade, Efat Jokar, Amir Fathi, Sue-min Chang, and Eric Wei-Guang Diau
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b11089 • Publication Date (Web): 04 Dec 2019
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Page 1 of 21 Journal of the American Chemical Society
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Mechanism of Photocatalytic CO2 Reduction by Bismuth-Based Perovskite
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Nanocrystals at the Gas-Solid Interface
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10 Sumit S. Bhosale,1 Aparna K. Kharade,2 Efat Jokar,1,3 Amir Fathi,1 Sue-min Chang2 and
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12 Eric Wei-Guang Diau1,3*
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14 Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung
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University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan.
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18 Institute of Environmental Engineering, National Chiao Tung University, Hsinchu, 30010,
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Taiwan.
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22 Center for Emergent Functional Matter Science, National Chiao Tung University, 1001
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Ta-Hsueh Rd., Hsinchu 30010, Taiwan; E-mail: diau@mail.nctu.edu.tw
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Abstract
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29 We report here a series of non-toxic and stable bismuth-based perovskite nanocrystals
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31 (PeNCs) with applications for photocatalytic reduction of carbon dioxide to methane and carbon
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33 monoxide. Three bismuth-based PeNCs of general chemical formulae A3Bi2I9, in which cation A+
34 = Rb+ or Cs+ or CH3NH3+ (MA+), were synthesized with a novel ultra-sonication top-down method.
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36 PeNC of Cs3Bi2I9 had the best photocatalytic activity for the reduction of CO2 at the gas-solid
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38 interface with formation yields 14.9 µmol g-1 of methane and 77.6 µmol g-1 of CO, representing a
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much more effective catalyst than TiO2 (P25) under the same experimental conditions. The
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41 products of the photocatalytic reactions were analyzed using a gas chromatograph coupled with a
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43 mass spectrometer (GC-MS). According to electron paramagnetic resonance (EPR) and diffuse-
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45 reflectance infrared spectra, we propose a reaction mechanism for photoreduction of CO2 via Bi-
46 based PeNC photocatalysts to form CO, CH4 and other possible side products.
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Journal of the American Chemical Society Page 2 of 21
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3 Introduction
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5 Because the demand for energy is strong, the rapidly increasing consumption of limited
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7 fossil fuels causes depletion of these traditional sources of energy and releases CO2 into the
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atmosphere, resulting in global warming. Among all solutions to decrease the amount of CO2 in
10 the atmosphere, the conversion of CO2 into fuels through artificial photosynthesis seems to be a
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12 promising approach. Much effort has been exerted to develop effective, environmentally
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14 compatible and stable photocatalysts. Various semiconductors with varied chemical and crystal
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structures have been investigated for the photocatalytic reduction of CO2.1-4 The size and shape of
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17 the catalyst particles are two key factors for the catalytic performance, which have been widely
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19 studied.3 On decreasing the size of the catalyst particle to a nanometer scale, new catalytic function
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21 has appeared with great performance.4
22 Organic-inorganic hybrid perovskites are promising semiconductors with outstanding
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24 optical and electrical properties that have been employed in such applications as solar cells,5–7
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26 light-emitting diodes,8–12 photon detectors,13,14 lasers15–17 among others.18 The popularity of the
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use of perovskites is attributed to their tunable optoelectronic properties, cost effectiveness and
29 solution-based fabrication. On decreasing the size of perovskite materials to form perovskite
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31 nanocrystals (PeNCs), the photoluminescence quantum yield (PLQY) becomes enhanced with the
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33 advantages of a large surface area and excellent stability. Lead (Pb)-based PeNCs have been
34 studied for photocatalysis.19,20 PeNCs of high quality can be fabricated with hot injection,21 ligand-
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36 assisted reprecipitation (LARP)22 and top-down methods.23 CsPbBr3,20 hybrid CsPbBr3/GO19
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38 composite and a CsPbBr3/metal-organic framework (MOF)24 were utilized for the photocatalytic
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reduction of CO2. Although these photocatalysts demonstrated effective CO2 conversion, the
41 toxicity of lead to human life due its high solubility in water limits their potential for widespread
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43 application. An alternative option to replace of lead is tin (Sn) in PeNCs, but tin-based PeNCs
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45 suffer instability and small PLQY.25 In contrast, bismuth (Bi)-based PeNC of general chemical
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formula A3Bi2I9 (cation A can be K+, Rb+, Cs+ or methylammonium MA+) provide a non-toxic
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48 and chemically stable alternative for photocatalytic applications.26 Bismuth perovskites have been
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50 applied as solar cells; the best Cs3Bi2I9 device attained efficiency of power conversion (PCE) only
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52 1.09 %27 and for MA3Bi2I9 3.17 %.28 These A3Bi2I9 compounds have structures of two types:
53 K3Bi2I9 and Rb3Bi2I9 have 2D defect-perovskite structures with corrugated layers of corner-
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55 connected Bi–I octahedra, whereas Cs3Bi2I9 and MA3Bi2I9 possess a zero-dimensional structure
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58 2
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1
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3 with isolated Bi2I93− ions forming face-sharing Bi–I octahedra.29 Although Bi-based PeNCs were
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5 synthesized with a LARP method30,31 with satisfactory stability, the PLQY was still less than that
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7 of their Pb-based analogues.
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In this work, we applied for the first time a top-down method to synthesize three Bi-based
10 PeNCs – namely Rb3Bi2I9, Cs3Bi2I9 and MA3Bi2I9, for photoreduction of CO2 to CO and CH4 at a
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12 gas-solid interface; the synthetic approach is schematically demonstrated in Figure 1. We report
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14 here not only a new approach to synthesize Bi-based PeNCs but also a detailed reaction mechanism
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of CO2 reduction using halide perovskite PeNCs as photocatalysts. CO2 was reduced
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17 photochemically to generate end products CO and CH4; the photocatalytic activity of Bi-based
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19 photocatalysts shows a trend Cs3Bi2I9 > Rb3Bi2I9 > MA3Bi2I9 >> TiO2. Electron paramagnetic
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21 resonance (EPR) and diffuse-reflectance infrared spectra were recorded to explain the effect of the
22 cation in the photocatalytic reaction; on this basis we propose a mechanism of CO2 reduction with
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24 PeNCs. We further show that CO2 photoreduction follows one of two paths, identifiable through
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26 either a formate or carbonate intermediate. The results show that the cation (in site A) and the
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crystal structure are important factors affecting the catalytic activity.
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45 Figure 1. Schematic representation of the top-down method to fabricate bismuth-based perovskite
46 nanocrystals, and its application in the solid-gas photocatalytic reduction of carbon dioxide.
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1
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3 Results and Disscusion
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Although the top-down method was reported for Pb-based PeNC,23 according to our
7 knowledge this report is the first to describe Bi-based PeNCs produced with an ultrasonic top-
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9 down method. Moreover, we used these PeNCs as efficient photocatalysts for CO2 reduction. Bulk
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11 perovskite crystals were formed on simply grinding the precursors (Figure 1) in the presence of
12 DMF (a few drops); the bulk perovskites were fragmented with an ultra-sonication method. The
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14 obtained PeNCs were protected with oleic acid (OA) and oleylamine (OLA) ligands present in the
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16 original precursor solution. As the preparation of PeNC involves irregular breaking of bulk
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perovskite crystals, the obtained PeNC have varied shapes and sizes on a nanometer scale. The
19 morphology, crystallinity and size distribution of PeNC for Rb3Bi2I9, Cs3Bi2I9 and MA3Bi2I9 were
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21 observed with a trasmission electron microscope (TEM), as shown in Figures 2a-c, respectively.
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23 The average crystal diameter was 12.6, 6.2 and 7.6 nm for Rb3Bi2I9, Cs3Bi2I9 and MA3Bi2I9 PeNCs,
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respectively. TEM images in Figure S1, supporting information (SI), were used to determine the
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26 size distribution.
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28 Powder X-ray diffraction (XRD) patterns for A3Bi2I9 (A = Rb+, Cs+ and MA+) PeNCs are
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30 shown in Figures 2d-f. XRD patterns were matched with standard XRD data reported for bulk
31 structures.27,32 Cs3Bi2I9 and MA3Bi2I9 PeNCs adopt a hexagonal structure of space group
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33 P63/mm;27 Rb3Bi2I9 has a monoclinic structure of space group P21/n.32 The broad background
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35 originated from organic ligands; a slight shift and peak broadening are attributed to the
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nanocrystaline nature of the PeNC.33 The elemental composition was analyzed with X-ray
38 photoelectron spectra (Figure S2, SI); as shown in Figures S2a–c, SI, these data exhibit Bi 4f
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40 signals at 159 and 164 eV, C 1s at 185 eV, N 1s at 400 eV and I 3d at 630 and 618 eV. For the
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42 Cs3Bi2I9 sample, Cs 3d signals at 726 eV, and for the Rb3Bi2I9 sample Rb at 112 eV were detected.
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Carbon, nitrogen, bismuth and iodine were common to all samples; capping organic ligands
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45 contribute to these signals of carbon and nirogen. As reported elsewhere,31 for Bi-based PeNCs,
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47 the surface composition of bismuth varies with particle size.
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17 (d) (f)
(006)
(e) *
(201)
(006)
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(600)
(502)
Intensity /a.u.
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21
(021)
(004)
(215)
22
(105)
(110)
(112)
(023)
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(025)
(004)
(042)
(015)
(044)
(023)
(045)
(136)
(011)
(043)
(010)
(204)
(022)
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(210)
(312)
(203)
* * * *
(208)
* * *
25 * *
26 10 15 20 25 30 35 40 10 15 20 25 30 35 40 10 15 20 25 30 35 40
27 2deg 2deg 2deg
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30 Figure 2. TEM images and size distribution of (a) Rb3Bi2I9 (b) Cs3Bi2I9 (c) MA3Bi2I9 and X-ray
31 diffraction patterns of (d) Rb3Bi2I9 (e) Cs3Bi2I9 (f) MA3Bi2I9. Symbol * denotes diffraction signals
32 of the ITO substrate.
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34 The optical properties of PeNCs in colloidal solutions and in spin-coated films were analyzed.
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36 The absorption spectra of PeNC solutions show excitonic transitions centered at 504, 498 and 506
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38 nm for Rb3Bi2I9, Cs3Bi2I9 and MA3Bi2I9, respectively (Figure 3). The photoluminescence (PL)
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spectra of Rb3Bi2I9, Cs3Bi2I9, and MA3Bi2I9 PeNC solutions showed maximum intensities at 558,
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41 578 and 575 nm, respectively. According to optical characterizations of PeNC solid films (Figure
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43 S3, SI), their emission spectra show bathochromic shifts from solution samples, indicating an
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45 aggregation of PeNCs in thin-film samples, but the PL spectra of PeNCs have two features that
46 indicate the existence of both direct and indirect band gaps near 298 K.34 To understand the charge-
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48 carrier kinetics, we measured transient PL decays; the PeNC samples were excited at 375 nm. The
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50 PL decays were monitored at the corresponding emission maxima of the PeNC solutions.
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1
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4 (a) (b)
5 1.0 Absorption 1.0 Absorption
Emission
6 Emission
7 0.8 0.8
Intensity /a.u.
Intensity /a.u.
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9 0.6 0.6
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11 0.4 0.4
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13 0.2 0.2
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15 0.0 0.0
300 400 500 600 700 800 300 400 500 600 700 800
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17 Wavelength /nm Wavelength /nm
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19 1
Normalized PL Intensity
1.0 Absorption Rb3Bi2I9
20 Emission Cs3Bi2I9
Intensity /a.u.
21 0.8 MA3Bi2I9
22 IRF
23 0.6
24 0.1
25 0.4
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30 300 400 500 600 700 800 0 2 4 6 8 10 12 14
31 Wavelength /nm Time /ns
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34 Figure 3. Steady-state absorption and PL spectra of PeNCs; (a) Rb3Bi2I9, (b) Cs3Bi2I9 and (c)
35 MA3Bi2I9; (d) transient PL decay profiles of PeNCs as indicated.
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37 All PL decays were fitted with a tri-exponential decay function; the corresponding fitting
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39 parameters are listed in Table S1, SI. The first decay components () are limited to almost the
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pulse duration for all three samples, but the amplitudes show the order MA3Bi2I9 > Cs3Bi2I9 >
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42 Rb3Bi2I9. This rapid decay component is attributed to trap-state relaxation.30 The Rb3Bi2I9
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44 sample is hence expected to have fewer bulk trap states inside the PeNC than the other samples
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46 according to the trend of the amplitude of . The second decay components () is assigned to
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recombination of surface defects.31  showed a trend Rb3Bi2I9 ~ Cs3Bi2I9 > MA3Bi2I9 with the
49 corresponding amplitudes showing the trend Rb3Bi2I9 > Cs3Bi2I9 > MA3Bi2I9. The Rb3Bi2I9
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51 sample is hence expected to undergo slower recombination of surface defects than the others;
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53 the MA3Bi2I9 sample might suffer from charge recombination on the surface. The third
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component () might be assigned to the radiative charge recombination on a scale of tens of
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1
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3 nanoseconds, but its contribution (~0.04) was small for all three samples because of significant
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5 contributions from bulk trap-state relaxation () and surface defect-state recombination ().
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7 As a result, the overall average PL lifetimes (PL) show the trend Rb3Bi2I9 > Cs3Bi2I9 > MA3Bi2I9.
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9 Before proceeding toward photocatalytic reduction of carbon dioxide, we tested the stability
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of PeNC films in severe conditions of humidity and illumination. We compared the XRD patterns
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12 of fresh samples (Figure S4, SI) with the patterns of samples kept for seven days in ambient
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14 conditions, RH = 70 %. The same samples, after seven days of ageing, were illuminated with a
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16 UV lamp (80.4 W cm-2) for 12 h. No significant change was observed in the XRD patterns,
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especially for PeNCs with inorganic cations. We thus conclude that the PeNCs were stable during
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19 the period of photoreduction.
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21 Bi-based materials like as bismuth oxyhalides have been extensively used in photocatalytic
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23 and electrocatalytic reduction of CO2.35–37 The incorporation of defects in the material to enhance
24 the photocatalytic activity was observed such that defects increased the adsorption of CO2 and
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26 trapping of excited electrons.37–39 The crystal structure of the catalyst is another factor to be
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28 considerred to improve its photocatalytic activity.40 According to this criterion Bi-based defect
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halide perovskites (A3M2X9) that form zero-dimensional and monoclinic crystals32 are excellent
31 candidates for photocatalytic reduction of CO2. We applied Bi-based PeNCs as photocatalysts to
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33 investigate the reduction of CO2 at a gas-solid interface, whereas a gas-liquid inteface faces
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35 problems of limited solubility of CO2 and detrimental products produced via photoreaction of the
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solvent molecules. For instance, the most commonly used solvent, ethyl ethanoate, can be
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38 decomposed into CO and CH4 via its own photoreaction with UV light.41 The ultraviolet
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40 photoelectron spectral data in Figure S5, SI, indicate that the energy levels of all three PeNCs are
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42 suitable for CO2 reduction.36,42 In our experiments, we loaded the PeNCs, as prepared, at the
43 bottom of a quartz reactor. N2 gas was passed for 60 min to remove air and to ensure that the
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45 reaction system was under anaerobic conditions. CO2 (99.9 %) was bubbled through water to
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47 generate a mixture of CO2 and H2O vapor. A lamp (32W UV B, 305 nm) served as a light source
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with intensity 80.4 μW cm-2 to reduce CO2 in a batch reactor (Figure S6, SI). The gaseous products
50 in the photoreactor were analyzed at interval 1 h with a gas chromatograph (GC). As the detector
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52 applied flame ionization (FID), the detection of carbon monoxide was impracticable; for this
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54 reason, only product yields of methane were determined as a function of duration of irradiation
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from 0–10 h; the results appear in Figure 4a.
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(a) (b)
20
6 Rb3Bi2I9 80
7 18 CH4
Cs3Bi2I9
Product Yield /mol g-1

8 70 CO
Methane /mol g-1
16 MA3Bi2I9
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14 P25 (TiO2) 60
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11 12 50
12 10
13 40
14 8
30
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16 20
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18 2 10
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20 0 1 2 3 4 5 6 7 8 9 10 Rb3Bi2I9 Cs3Bi2I9 MA3Bi2I9 P25 (TiO2)
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Time /h
23 Figure 4. (a) Product yields of methane production with catalysts at each hour of reaction (detected
24 with GC-FID); (b) comparison of production of methane and carbon monoxide during
25 photochemical reaction for 10 h (detected with GC-MS).
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28 Figures S7-S9, SI, show the GC-MS results of the three PeNCs. The retention periods for
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30 the formation of methane and CO are about 3.6 and 4.7 min, respectively. For the mass spectra,
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the major signals at m/z 16.1 and 28.1 are assigned to CH4 and CO, respectively. Figure 4b shows
33 the amounts of methane and carbon monoxide produced via UV-irradiation for period 10 h and
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35 detected with GC-MS. The greatest yield of methane, 17.0 ± 1.6 µmol g-1, was observed for
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37 Rb3Bi2I9 PeNC, whereas 14.9 ± 0.8 and 9.8 ± 0.6 µmol g-1 were observed for Cs3Bi2I9 and
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MA3Bi2I9 PeNCs, respectively. CO was detected in the reaction system via GC-MS; the formation
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40 of CO attained the greatest level for Cs3Bi2I9 PeNC (77.6 µmol g-1); only 18.2 and 7.2 µmol g-1
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42 were observed for Rb3Bi2I9 and MA3Bi2I9, respectively. It is remarkable to note that the formation
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44 yield of CO using Cs3Bi2I9 PeNC has reached a new record as compared to those using the other
45 photocatalysts summarized in Table S2, SI.
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47 We carried out GC-MS studies for the following two points. First, the product yields were
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49 compared with those of P25 TiO2, which serves as a standard for the photoreduction of CO2 to
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form methane.2 All Bi-based PeNCs acted as superior photocatalysts, producing methane 10–20
52 times as great as that of P25. Second, we undertook three control experiments to confirm that CH4
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54 and CO were produced from CO2 photoreduction: (i) reaction in the presence of catalyst, CO2 and
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56 water in dark conditions; (ii) reaction with catalyst and water under irradiation but in the absence
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3 of CO2; (iii) reaction with CO2 and water under irradiation but in the absence of catalyst. No
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5 photoproducts were detected in these three control experiments. For example, Figures S10a-c, SI,
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7 show the GC-MS results under condition (ii) for catalysts Rb3Bi2I9, Cs3Bi2I9 and MA3Bi2I9,
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respectively. In the absence of CO2, no photoproduct was observed, indicating that no
10 photodegradation of the organic ligands surrounding the PeNC catalysts occurred during the period
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12 of illumination. Control experiments were also undertaken for CO2 reduction at a gas-liquid
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14 interface using ethyl ethanoate as solvent.19,20,26 Our results indicated that large amounts of
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methane and carbon monoxide for the system were produced in the absence of CO2 and
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17 photocatalyst PeNC under illumination at 305 nm for 10 h. Figure S11, SI, shows the GC-MS
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19 results for these control experiments, which show clearly that solvent ethyl ethanoate can undergo
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21 photodegradation to form methane and carbon monoxide. Ethyl ethanoate is hence unsuitable for
22 use in the gas-liquid reaction whereas the gas-solid reaction is appropriate to study photocatalytic
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24 reduction of CO2.
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26 8
2.002
(a)
27
2.022
2.013
6
2.008
1.991
1.992
1.982
1.996
28 4
29
EPR Derivative Signal /103 a.u.
2
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0
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32 -2
2.002
33 15 (b)
2.009
2.013
2.022
2.026
1.996
34 10
1.99
35 5
36 0
37 -5
38 -10
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2.002
4 (c)
2.013
1.998
2.009
2.022
1.996
1.982
1.99
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41 2
42 0
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44 -2
45 3400 3420 3440 3460 3480
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Magnetic Field /G
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Figure 5. Electron paramagnetic resonance (EPR) spectra of (a) Rb3Bi2I9, (b) Cs3Bi2I9 and (c)
50 MA3Bi2I9 under illumination for 1 h in the absence (solid curves) or presence (dashed curves) of
51 CO2 and H2O. The vertical dashed lines show the corresponding g-factor values.
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53 Electron paramagnetic resonance (EPR) spectra were recorded for samples in toluene
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solution at 77 K for each catalyst under illumination in the presence or absence of CO2 and H2O
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56 vapors to examine charge trapping and interfacial charge transfer. Figure 5 shows the EPR data in
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1
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3 vacuum (solid curves) and in the presence of CO2 and H2O (dashed curves). As suitable EPR
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5 references were unavailable for lead-free perovskites, we compared the derivative signals of Bi
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7 perovskite EPR spectra with those of lead halide and organic lead halide perovskites.43 According
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9
to the EPR spectra of a lead halide, electrons and holes are trapped by lead cations; the Pb3+ cation
10 can stabilize holes to become EPR-active. Electrons are trapped in an EPR-inactive species. In an
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12 organic lead halide perovskite, electrons are trapped by the Pb2+ species to become EPR-inactive
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14 whereas the EPR-active holes are trapped by the Pb3+ species and the organic cations.43
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Accordingly, the EPR results shown in Figure 5 indicate the amounts of EPR-active holes under
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17 illumination with a trend Cs3Bi2I9 > Rb3Bi2I9 > MA3Bi2I9 in the absence of CO2 and H2O. When
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19 CO2 and H2O vapor was added to the system, the reduction of CO2 in the presence of H2O
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21 proceeded to quench the EPR-active holes with the same trend of photoactivity as that of EPR-
22 activity shown in Figure 5. As a control experiment, Figure S12, SI, shows the enhanced EPR
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24 activity when the three PeNC catalysts were exposed to light compared to their dark conditions.
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26 Our results indicate that Cs3Bi2I9 exihibts a superior ability to generate electron and hole pairs
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relative to the other PeNCs. In general, Bi-based perovskites are expected to accept defect-tolerant
29 electronic structures in which the conduction and valence bands are formed with antibonding
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31 orbitals.44 Similar to the effect of lead perovskites, we expect that Bi-based perovskites can
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33 stabilize excited electrons with Bi3+ and holes with Bi4+ as in the cases of AgX and PbX2 crystals
34 (X represents a halide).43
35
36 EPR spectra were recorded also in the absence of ligands to clarify that the EPR signals are
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38 generated from the active holes upon irradiation. Figures S13a-d, SI, show no EPR signal from
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bulk perovskites and BiI3 other than MA3Bi2I9 (Figure S13c), indicating that quenching is more
41 rapid in the absence of ligands for bulk Rb3Bi2I9, Cs3Bi2I9 and BiI3.30 In contrast, bulk MA3Bi2I9
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43 displays intense EPR signals attributed to ● CH2NH3+ radicals that represent trapping of holes by
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45 this organic cation.43 In Figure 5, g-factor 2.002 indicates that the holes can be stabilized by Bi4+;
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the presence of hyperfine splitting in the EPR signals was due to the unpaired electrons located on
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48 oxygen ions of the oleic acid.45 According to our observation of Rb3Bi2I9 and Cs3Bi2I9, holes are
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50 efficiently stabilized by Bi4+ and oxygen ions, but, for MA3Bi2I9, holes are stabilized by Bi4+, ●
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52 CH2NH3+ radical cations and oxygen anions. The transfer of the holes into water (the oxidation
53 channel) is hence inefficient for MA-based PeNC, which results in decreased quenching of the
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55 EPR signal shown in Figure 5c. This effect has made MA3Bi2I9 a poorer photocatalyst than the
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58 10
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1
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3 other two PeNC catalysts, consistent with the results shown in Figure 4. In addition, Cs3Bi2I9 PeNC
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5 exhibits the greatest photocatalytic activity because of its superior charge generation and efficient
6
7 charge transfer in the presence of CO2 and H2O. The crystal structure of Cs3Bi2I9 can also support
8
9
its high catalytic activity. Rb3Bi2I9 adopts a crystal structure of type distorted-defect variant
10 perovskite (A3M2X9) for which every third M layer of the perovskite in facet [001] is depleted.32
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12 As bismuth constitutes the active site of the catalyst, the depletion of bismuth in Rb3Bi2I9 thus
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14 decreases the photocatalytic activity relative to Cs3Bi2I9.
15
We recorded diffuse-reflectance infrared spectra to understand the reaction mechanism for
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17 CO2 reduction using PeNC in this series as photocatalysts. These spectra were recorded under
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19 diffuse-reflection conditions; the surface-adsorbed chemical species were analyzed through
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21 examination of the infrared signals following illumination. The illumination time was varied to
22 study intermediate steps in the catalytic process, with results shown in Figure S14, SI. Figure 6
23
24 shows spectra after illumination for 300 min for the three catalysts with various steady-state
25
26 intermediate species labeled as indicated in the caption.
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28
29 (e) (i)
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31
(c)
32
(a) (b) (d) (g) (j)
Absorbance
33 (k)
(f) (h) Rb3Bi2I9 (l)
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37
Cs3Bi2I9
38
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40 MA3Bi2I9
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42 3600 3400 3200 3000 2800 2600 1800 1600 1400 1200 1000
43 -1 -1
44 Wavenumber /cm Wavenumber /cm
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46 Figure 6. Diffuse-reflectance infrared spectra of Rb3Bi2I9 (blue), Cs3Bi2I9 (red) and MA3Bi2I9
47
48 (black) in the presence of CO2 and H2O under illumination for 5 h. Chemical species observed in
49 these spectra are assigned as (a) free –OH, (b) H-bonded –OH, (c) and (k) formate,46 (d) bridge
50 carbonate,47 (e) dioxycarbon anion,48 (f) and (i) monodentate carbonate,47,49,50 (g) and (j) bidentate
51
52 carbonate,51–53 (h) bicarbonate and (l) methoxy.46
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54
55
56
57
58 11
59
1
2
3 Bands (a) and (b) in the spectra show free OH and H-bonded OH vibrations, respectively,
4
5 but only Rb3Bi2I9 displays the free OH vibrational feature because of its layer-defect crystal
6
7 structure. Upon photoreduction of CO2, the surfaces of these PeNC catalysts became covered with
8
9
the hydroxyl group, so to exhibit a hydrophilic property. The intermediate species shown in Figure
10 6 provide crucial evidence for the photocatalytic reaction. First, the pronounced formation of lines
11
12 (e) and (c) in Rb3Bi2I9 indicates that dioxycarbon anion and formate might be the most significant
13
14 intermediates for CO2 reduction, and that the mechanism occurs via the monodentate channel
15
shown in Figure 7a. In contrast, for Cs3Bi2I9, spectral lines (d), (f) and (j) corresponded to the
16
17 formation of bridge carbonate, monodentate carbonate and bidentate carbonate, respectively. The
18
19 CO2 reduction with a Cs3Bi2I9 PeNC catalyst might hence follow a bidentate channel shown in
20
21 Figure 7b. Second, in both monodentate and bidentate channels, formate is the key intermediate
22 for the photoreduction of CO2 to form both CO and methane. The formation of methane is an eight-
23
24 electron process from CO2; the reaction mechanism to form methane from formate is shown in
25
26 Figure 7c. As a result, the infrared intensity of formate shows a trend Rb3Bi2I9 > Cs3Bi2I9 >
27
28
MA3Bi2I9, which is consistent with the trend of the methane product yields shown in Figure 4.
29 Third, the side reactions for the formation of formic acid (a two-electron process), formaldehyde
30
31 (a four-electron process) and methanol (a six-electron process) are shown in Figure 7d. As we
32
33 observed no side product in our GC-MS system, these side reactions were dark; the formation of
34 only CO and methane was observed, as discussed above.
35
36
37 Our Bi-based PeNCs were composed of corner-sharing BiI6 octahedra; these octahedra are
38
39
situated at the surface of PeNC so to facilitate the attachment of ligands OA and OLA.29,31 BiI6
40 acts as a Lewis acid and forms a donor-acceptor complex with CO2, which results in chemisorption
41
42 of CO2 from the oxygen side. CO is the primary product, which requires only two electrons to
43
44 form via either a monodentate or a bidentate channel shown in Figure 7. We emphasize that
45 Cs3Bi2I9 exhibited the best photocatalytic activity (Figure 6), which is consistent with the greatest
46
47 product yield of CO formation (Figure 4b) for this catalyst. As the major path for formation of CO
48
49 and methane is via the bidentate channel for Cs3Bi2I9, the large amount of CO might be produced
50
51 via the monodentate channel through the dioxycarbon radical bypass channel shown in Figure 7a.
52 This inference is based on the appearance of the dioxycarbon anion intensity, which is smaller for
53
54 Cs3Bi2I9 than for Rb3Bi2I9. Both monodentate and bidentate channels contribute to the formation
55
56 of CO for Cs3Bi2I9, as rationalized for its large yield of CO mentioned above.
57
58 12
59
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Figure 7. Plausible mechanism of photoreduction of CO2 via Bi-based PeNC catalysts.
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58 13
59
1
2
3 Conclusion
4
5
6
We demonstrated a novel top-down synthetic method via ultra-sonication to make three
7 bismuth-based PeNC materials and have shown their potential application in the photoreduction
8
9 of carbon dioxide at the gas-solid interface to generate carbon monoxide and methane as products.
10
11 We analyzed the photoproducts and conducted control experiments with a gas chromatograph and
12 a mass spectrometer. The yields of product CO exhibit the trend Cs3Bi2I9 >> Rb3Bi2I9 > MA3Bi2I9
13
14 >> TiO2 whereas those of methane show the trend Rb3Bi2I9 > Cs3Bi2I9 > MA3Bi2I9 >> TiO2.
15
16 Electron paramagnetic resonance (EPR) and diffuse-reflectance infrared spectra were recorded to
17
18
explain the varied photocatalytic activity of these three PeNC photocatalysts. A superior charge
19 transfer in Cs3Bi2I9 and restricted charge transport in MA3Bi2I9 were deduced from the EPR results.
20
21 From a careful analysis of the infrared spectra we propose a complete reaction mechanism for the
22
23 reduction of CO2 using Bi-based PeNC catalysts to rationalize the observed trends of the yields of
24
both CO and methane. These Bi-based PeNCs have large bandgaps in the visible region with great
25
26 binding energies so that they may have the potentials to serve for other optoelectronic applications.
27
28
29
30 Supporting Information. Experimental details, fourteen supplementary figures and two
31 supplementary tables are supplied in Supporting Information.
32
33
34
35 Acknowledgements
36
37
Ministry of Science and Technology (MOST) in Taiwan provided financial support of this
38 research (MOST 105-2119-M-009-011-MY3, MOST 107-2119-384 M-009-001 and MOST
39
40 108-2119-M-009-004). This work was also financially supported by the Center for Emergent
41
42 Functional Matter Science (CEFMS) of National Chiao Tung University (NCTU) from The
43
Featured Areas Research Center Program within the framework of the Higher Education
44
45 SPROUT Project by the Ministry of Education (MOE) in Taiwan.
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58 14
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Based Perovskite Nanocrystals at the Gas-Solid Interface

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

Product Yield /mol g-1

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