AgVO3 Nanoribbon Heterojunctions with

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Ba5Ta4O15 Nanosheets/AgVO3 Nanoribbons Heterojunction with Enhanced Photocatalytic Oxidation Performance: Holes Dominated Charge Transfer Path and Plasmonic Effect Insight Kai Wang, Xiaoyong Wu, Gaoke Zhang, Jun Li, and Yuan Li ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b00477 • Publication Date (Web): 12 Apr 2018 Downloaded from http://pubs.acs.org on April 13, 2018

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ACS Sustainable Chemistry & Engineering

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Ba5Ta4O15 Nanosheets/AgVO3 Nanoribbons

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Heterojunction with Enhanced Photocatalytic

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Oxidation Performance: Holes Dominated Charge

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Transfer Path and Plasmonic Effect Insight

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Kai Wang1, Xiaoyong Wu1, Gaoke Zhang1,2*, Jun Li1, Yuan Li1

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1

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and Environmental Engineering, Wuhan University of Technology, 122 Luoshi Road, Wuhan

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430070, People’s Republic of China

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2

Hubei Key Laboratory of Mineral Resources Processing and Environment, School of Resources

State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology,

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Wuhan 430070, China

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Corresponding Author:

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E-mail: [email protected]

13 14

ACS Paragon Plus Environment

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ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Abstract

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Heterojunction photocatalysts for environmental pollutant removal have attracted great attention

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because of their excellent photocatalytic efficiency. In this study, we report a novel

4

Ba5Ta4O15/AgVO3 heterojunction photocatalyst with excellent photocatalytic activity, which was

5

synthesized by facile two-step self-assembly strategy. Transmission electron microscopy (TEM)

6

reveals that Ba5Ta4O15 nanosheets adhered to the surface of AgVO3 nanoribbons to form

7

Ba5Ta4O15/AgVO3

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photocatalytic activities for the Acid Red G (ARG) degradation, which are almost 2.7 times

9

higher than that of AgVO3. The trapping experiments, electrochemical analysis and ESR

10

analyses altogether indicate that the boosting photocatalytic performance could attribute to the

11

synergy effect of the holes dominated charge transform path and localized surface plasmon

12

resonance (LSPR). Finally, a possible photocatalytic mechanism of the photocatalytic progress

13

was discussed. This study might provide the novel strategy toward designing high efficient

14

heterojunction photocatalyst systems for pollutant degradation and environmental remediation.

15

Keywords: Ba5Ta4O15 Nanosheets, AgVO3 Nanoribbons, Heterojunction, Photocatalytic

heterojunction.

The

as-obtained

photocatalysts

exhibited

enhanced

16


2

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1

Introduction

2

With increasing requirements for environmental remediation and alternative energy exploration,

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tremendous effort has been dedicated to the utilization of solar energy.1-3 Being a kind of

4

environment friendly technology, semiconductor photocatalysis technique has aroused pervasive

5

public concern and been successfully applied to the degradation of toxic and hazardous organic

6

pollutants.4-6 Nevertheless, the practical applications of most photocatalysts were inhibited by

7

some drawbacks, such as the inefficient visible light absorption, the lower photogenerated

8

carriers’ separation and the lack of active species generation.7 Heterojunction semiconductor

9

system is an feasible method to resolve these problems, which can extend the visible light range

10

absorption and restrain photogenerated carriers’ recombination.8,9

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Among various photocatalysts, layered perovskite materials, especially tantalum-based

12

nanocomposites with attractive crystal structures and high negative charge density often exhibit a

13

high electrical conductivity and photoresponse for the photocatalytic degradation of pollutants.10

14

Tantalum-based semiconductors possess conduction bands (CB) forming from a Ta 5d orbital

15

located at a more negative position than Nb 4d.11 Many metal oxide nanocomposites containing

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Ta5+ ions have been studied recently. Zhu et al synthesized monolayer tantalates nanosheets with

17

hexagonal structure by a facile hydrothermal progress and Zhou et al demonstrated a series of

18

A5B4O15 (A=Ca, Sr, Ba; B=V, Nb, Ta) layered perovskite materials through theoretical

19

calculations.12-13 However, the tantalum-based layered perovskite nanomaterials with high

20

photocatalytic activity are still worthy to be developed. Sun et al reported the advantage of two-

21

step self-assembly strategy and the self-assembly progress is a practicable method to design

22

multiscale heterojunction nanostructures. 14 It might be good way to accelerate the photocatalytic

23

performance of the Ba5Ta4O15 by constructing heterojunction photocatalysts system.


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Page 4 of 37

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Various silver-based nanomaterials have attracted widespread attention owing to their

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potential applications in the field of photoelectrochemistry. As a typical silver-based

4

photocatalyst, AgVO3 has been demonstrated to be a high performance visible light responsive

5

photocatalyst, due to its well crystallization and suitable band gap.15-16 Because of the unique

6

band structure, the Ag 4d, V 3d and O 2p orbits constitute a highly hybridized valence band

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together, which supports the maneuverability of photogenerated holes (h+).17,18 However, similar

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to many silver-based photocatalysts, low quantum efficiency and limited visible light absorption

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efficiency are still challenges huge to ameliorate the photocatalytic activity of AgVO3 in order to

10

solve the practical environmental requirements.19-22 Recently, some studies have focused on the

11

fabrication of silver vanadate-based heterostructure photocatalysts.23-25 Due to the limitation of

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silver vanadate-based composites, it is essentially necessary to find suitable components which

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play an effective role in modifying AgVO3 and improving its photocatalytic performance.

14

Herein, Ba5Ta4O15/AgVO3 heterojunction photocatalysts were prepared via a facile two-step

15

self-assembly strategy for the first time. The density of states and band energy of Ba5Ta4O15 and

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AgVO3 were also analysed by density functional theory computations and the photocatalytic

17

activity of the as-obtained samples towards ARG solution degradation was evaluated under the

18

visible light irradiation. Furthermore, holes mediated charge transfer mechanism and synergistic

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Ag plasmons effects for the boosting photocatalytic performances of the Ba5Ta4O15/AgVO3

20

heterojunction composites are proposed.

21 22 23


4

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1

Experimental

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Synthesis of nanocomposites: Ba(OH)2·8H2O, Ta2O5, AgNO3 and NH4VO3 were purchased

3

from Guoyao Chemical Reagent Co. Ltd. Ba5Ta4O15 nanosheets were synthesized via

4

hydrothermal process. 0.005 mol Ba(OH)2·8H2O was dissolved in 60 mL deionized water, then

5

0.002 mol Ta2O5 was added under stirring for 40 min and the white slurry was added into a PVP-

6

lined autoclave (90 mL) and heated at 270 °C for 48 h. The white products were washed and

7

dried at 70 °C for 8h. The Ba5Ta4O15/AgVO3 composites were synthesized through a two-step

8

hydrothermal treatment. Briefly, 20 mL of AgNO3 solution (0.05M) was prepared. Then,

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Ba5Ta4O15 (0.4 g, 0.2 g, 0.1 g, 0.05 g) were added to 20 mL NH4VO3 suspension (0.05 M) and

10

stirred for 1 h. After that, mixed suspension was added to the above AgNO3 solution and stirred

11

for 4h and the mixture was transferred into a PVP-lined autoclave and heated at 180 °C for 24 h.

12

The asymptotic yellow products were washed and dried at 70 °C for 12 h. The samples were

13

denoted as A/BTO-1, A/BTO-2, A/BTO-3, A/BTO-4 when the mass ratios of Ba5Ta4O15:

14

AgVO3 were 2:1, 1:1, 1:2 and 1:4, respectively. Under comparison, pure AgVO3 nanoribbons

15

were also synthesized under conditions identical to those of Ba5Ta4O15/AgVO3 without

16

Ba5Ta4O15.

17

Characterization: The morphology of the nanocomposites was obtained using a field emission

18

scanning electron microscopy (S4800, Hitachi) and the EDX-mapping was analysed by JEM-

19

7500F. The microstructure and crystallinity of nanocomposites were analyzed by X-ray

20

diffraction (XRD) with Cu Kα radiation. The absorption edges of as-prepared samples were

21

analysed by a UV-vis spectrophotometer (Lambda 750S). X-ray photoelectron spectra (Thermo

22

2000) were tested by spectrometer with Al Kα source and the binding energy of adventitious

23

carbon contamination taken to be 284.6eV. Raman spectra were analysed by a confocal laser


5


Page 6 of 37

1

Raman spectrometer (RENISHAW). Photoluminescence spectra were recorded on fluorescence

2

spectrophotometer (Shimadzu,

3

spectrophotometer were tested by Edinburgh Instruments. The ESR experiments was recorded on

4

an (ESR) electron paramagnetic resonance spectrometer (Bruker, A300). Photoelectrochemical

5

analysis was recorded on electrochemical workstation (CHI660E, Shanghai) in three-electrode

6

group and the electrolyte was 0.1M Na2SO4.

7

Photocatalytic activity and ESR experiments: The photocatalytic degradation of Acid Red G

8

(ARG) and ciprofloxacin (CIP) used a 300 W Xe lamp with a UV cutoff filter (λ ≥ 400 nm) as

9

visible light source. In a typical test, 50 mg photocatalyst was placed in 100 mL 20 mg/L

10

ARG/CIP solution. ARG/CIP solution was stirred in the dark for 60 min to reach the adsorption

11

equilibrium. The concentration of ARG and CIP was detected by UV–vis spectrophotometer

12

(UV751GD) at wavelength of 505 and 277 nm. In ESR experiments, the •O2- and •OH species

13

were detected by the dimethyl pyridine N-oxide (DMPO). Typically, 0.01 g of the photocatalysts

14

were dispersed completely in 1 mL of deionized water (•OH) or 1 mL of methanol (•O2-), and

15

0.04 mL of dimethyl pyridine N-oxide (DMPO) was injected under Xe lamp irradiation for 2, 10

16

min, respectively. Total organic carbon (TOC) was analysed by total organic carbon analyzer

17

(Elementar, Germany).

18

Theoretical Calculations: The electronic structure and density of states of Ba5Ta4O15 and

19

AgVO3 were calculated by the Vienna ab initio simulation package (VASP) code ground on

20

density functional theory (DFT) method. The exchange-correction function was depicted by the

21

Perdew-Burke-Ernzerhof (PBE) formulation of the generalized gradient approximation (GGA).

22

The cutoff energy of was 400 eV and the Brillion zone ware combined by Monkhorst-Pack

23

effected sets of k-points. The k-meshes 3×2×2 and 2×2×1 are used in the calculations of

RF-5301) and

the time-resolved


transient

PL decay

6

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Ba5Ta4O15 and AgVO3, respectively, which was sufficient to accomplish convergence for single-

2

cell calculations.

3 4

Results and discussion

5

Structure and morphology. The crystalline of the Ba5Ta4O15, AgVO3 and Ba5Ta4O15/AgVO3

6

composites were shown in Figure 1. As shown in Figure 1, 2θ degrees of 28.87o, 30.87o, 42.74o,

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53.55o could be ascribed to (103), (110), (203), (213) crystal planes of Ba5Ta4O15 (JCPDS: 18-

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0193). As depicted in Figure 1, 2θ values of 29.84o, 32.85o, 33.48o in the pattern of AgVO3 could

9

be ascribed to (501), (-411), (-112) crystal planes of AgVO3 (JCPDS: 86-1154).26 The XRD

10

patterns of Ba5Ta4O15/AgVO3 showed that Ba5Ta4O15 did not significantly change the structure

11

of AgVO3. The characteristic peaks of the AgVO3 were no found in the patterns of A/BTO-3 and

12

A/BTO-4 composite because of the low crystallinity of Ba5Ta4O15 nanosheets. Meanwhile, there

13

are no impurity was produced in the preparation process.

14 15

Figure 1. XRD patterns of Ba5Ta4O15, AgVO3 and a series of Ba5Ta4O15/AgVO3 composites.


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Page 8 of 37

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The morphologies of the as-obtained composites were studied by FESEM and TEM analysis.

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Figure 2a and b displays the images of AgVO3 nanoribbons and Ba5Ta4O15 nanosheets,

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respectively. The FESEM image of AgVO3 shows nanoribbon morphology with a size of 150 nm

4

in width and more than 6µm in length. As shown in Figure 2b, the pristine Ba5Ta4O15 has a

5

sheet-like

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Ba5Ta4O15/AgVO3 composites were also analyzed by FESEM (Figure S1). The FESEM image

7

displays a homogeneous distribution of Ag, V, Ba, Ta, and O elements in Ba5Ta4O15/AgVO3

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heterojunction. The EDX mapping image of Ag, and V could be observed to be the same shape.

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In addition, it could also be seen that Ba, and Ta elements adhered to the surface of AgVO3

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nanoribbons. For Ba5Ta4O15/AgVO3 composites, the morphology of AgVO3 was maintained and

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the detailed structural information was further detected by TEM analysis.27-28 As shown in Figure

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2c, Ba5Ta4O15 nanosheets are decorated on the surface of AgVO3 nanoribbons. The HRTEM

13

image of the Ba5Ta4O15/AgVO3 composites shows the distinct crystallographic planes of AgVO3

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and Ba5Ta4O15 (Figure 2d), in which a lattice spacing of 0.306 nm corresponds to the (501) plane

15

of the AgVO3 nanoribbons and the lattice spacings of 0.297 nm corresponds to the (110) planes

16

of the Ba5Ta4O15 nanosheets. These results further illustrate that the interaction between the

17

AgVO3 nanoribbons and the Ba5Ta4O15 nanosheets is strong.

structure

with

smooth

surface.

The

microstructure


and

composition

of

8

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Figure 2. FESEM image of (a) AgVO3; TEM images of (b) Ba5Ta4O15 and (c)

3

Ba5Ta4O15/AgVO3; HRTEM image of (d) Ba5Ta4O15/ AgVO3 heterojunction.

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To characterize the surface chemical state of Ba5Ta4O15/AgVO3 composites, XPS analysis of

5

the composite with A/BTO-3 was carried out. Figure 3a indicates that the Ba5Ta4O15/AgVO3

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composites are composed of Ba, Ta, Ag, V and O. The presence of C 1s peak (284.6 eV) might

7

be the adventitious hydrocarbon. In Figure 3b, the peaks at 779.6 and 795.1 eV are assigned to

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the Ba 3d5/2 and Ba 3d3/2 spin–orbital splitting photoelectrons of Ba2+ in the Ba5Ta4O15,

9

respectively. When Ba5Ta4O15 was introduced, the two peaks shifted to 368.00 and 374.03 eV in

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Ba5Ta4O15/AgVO3 composites, respectively. From Figure 3c, the values at 25.1 and 27.2 eV

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corresponds to Ta 4f7/2 and Ta 4f5/2 orbitals of Ta5+ in Ba5Ta4O15, respectively. Moreover, the

12

two peaks shifted to 25.4 and 27.5 eV in Ba5Ta4O15/AgVO3 composites, respectively. As shown

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in Figure 3d, two peaks at 367.5 and 373.5 eV are indexed to the binding energies of Ag+ 3d5/2

14

and Ag+ 3d3/2. The peaks of Ag+ 3d5/2 and Ag+ 3d3/2 for A/BTO-3 composites shifted to 367.8

15

and 373.8 eV, respectively. In Figure 3e, two peaks at 516.7 and 524.1 eV are attributed to the


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Page 10 of 37

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binding energies of V5+ 2p5/2 and V5+ 2p3/2 in AgVO3 composites shifted to 516.7 and 524.1 eV,

2

respectively. In all, the shifts in Ag 3d, V 2p, Ba 3d, and Ta 4f peaks indicate that the chemical

3

states in the Ba5Ta4O15/AgVO3 composites have changed after the introduction of Ba5Ta4O15

4

nanosheets and illustrate a strong interaction between Ba5Ta4O15 and AgVO3. Compared with the

5

O 1s peak of Ba5Ta4O15 and AgVO3, the main peak at 530 eV is assigned to the V–O bonds in

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the AgVO3 and the peak at 531.3 eV is related to the binding energy of Ta–O bonds along with

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the perovskite-like (Ta4O155-) layered structure of Ba5Ta4O15 in Ba5Ta4O15/AgVO3 composites.

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10

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Figure 3. XPS spectra of the Ba5Ta4O15, AgVO3 and A/BTO-3 composites: (a) survey spectrum

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of A/BTO-3 composites, (b) Ba 3d spectra of Ba5Ta4O15 and A/BTO-3 composites, (c) Ta 4f

3

spectra of Ba5Ta4O15 and A/BTO-3 composites, (d) Ag 3d spectra of AgVO3 and A/BTO-3

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composites, (e) V 2p spectra of AgVO3 and A/BTO-3 composites, and (f) O 1s spectra of the

5

Ba5Ta4O15, AgVO3 and A/BTO-3 composites.

6

Figure 4 demonstrates the Raman spectra of the Ba5Ta4O15, AgVO3 and A/BTO-3 samples.

7

For pure Ba5Ta4O15 sample, the peak at 318 cm-1 would be matched to O-Ta-O bending

8

vibrations in the TaO6 groups of Ba5Ta4O15 sample. The typical peak from 500 to 1000 cm-1

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might correspond to the stretching of the various Ta-O bonds. The peak at 788cm-1 is probably

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connected with the corner-sharing oxygen atoms. For AgVO3 nanoribbons, the strong peak at

11

892 cm-1 might root in Ag-O-V or O-V-O bending vibrations. The peak at 813 cm-1 can be

12

associated with the stretching vibrations of the Ag-O-Ag bridges and the V-O bond in the

13

metavanadate joints is explained by the 737 cm-1peak. The bands at 340 and 252 cm-1 are due to

14

asymmetric deformation patterns of the VO43- tetrahedron. Ba5Ta4O15/AgVO3 heterojunction

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indicates higher intensities than those of Ba5Ta4O15 and AgVO3, which could be result from the

16

effects of the strong Raman enhancement effect in the Ba5Ta4O15/AgVO3 heterojunction

17

system.20


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Page 12 of 37

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Figure 4. Raman spectra of the pure AgVO3, Ba5Ta4O15 and A/BTO-3.

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N2 adsorption–desorption characteristics of AgVO3, Ba5Ta4O15 and A/BTO-3 composite was

4

given in Figure S2. As displayed in Figure S2, typical IV isotherms with a typical H3 hysteresis

5

loop were clearly observed on three samples. The BET surface areas of the pristine AgVO3,

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Ba5Ta4O15, and A/BTO-3 are determined to be ca. 4.92, 12.37 and 8.36 m2/g, respectively.

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Moreover, the surface areas of the Ba5Ta4O15/AgVO3 composites were higher than that of pure

8

AgVO3 after the uniform growth of AgVO3 nanoribbons after introducing the Ba5Ta4O15

9

nanosheets. This suggests that the heterostructure with a higher surface area may provide more

10

active sites for adsorption and degradation of dye Acid Red G (ARG) solution, enhancing the

11

photocatalytic activity of the photocatalysts.

12

To explore the optical properties of the as-obtained composites, Figure 5a displays the UV–vis

13

diffuse reflectance spectra of Ba5Ta4O15, AgVO3 and Ba5Ta4O15/AgVO3 composites.29 The

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absorption edges of pure Ba5Ta4O15 and pure AgVO3 are approximately located at 340 and 636

15

nm respectively. The band edges of the Ba5Ta4O15/AgVO3 composites exhibited obvious red


12

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shift as compared to that of the bare Ba5Ta4O15. The band edge and optical absorption could be

2

followed by the formula:

3

αhv = A(hv-Eg)n/2

4

Thus, the band gap of the Ba5Ta4O15 and AgVO3 was calculated via a plot of the (Ahv)2 versus

5

hv. As displayed in Figure 5b, the Eg values of the Ba5Ta4O15 and AgVO3 were 3.63 eV and 1.95

6

eV respectively.

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Figure 5. (a) UV–vis diffuse reflectance spectra of Ba5Ta4O15, AgVO3 and a series of

9

Ba5Ta4O15/AgVO3 composites. (b) Plot of the (Ahv)2 versus hv for Ba5Ta4O15 and AgVO3.

10

Electronic property calculation. The band structure and destinies of states of Ba5Ta4O15 and

11

AgVO3 were analysed by DFT calculation.30-32 The building single unit cells were verified by

12

XRD analysis and the Ba5Ta4O15 and AgVO3 cell model is shown in Figure 6a and c. It can be

13

observed from the calculated band structure in Figure 6b that the band gap of Ba5Ta4O15 is 2.96

14

eV, which is an indirect gap semiconductor.13 The calculated Eg value of Ba5Ta4O15 tends to be

15

smaller than the experimental band gap (3.63 eV), owing to the limitation of the DFT

16

calculation.33-34 The lower valence band of Ba5Ta4O15 from -9 to -13 eV are essentially

17

supported to Ba 5p with a very small admixture of O 2p and Ta 5d. In addition, the upper

18

valence band from -6.1 eV to Fermi level is dominant by Ta 5d and O 2p orbitals. And the Ba


13


Page 14 of 37

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ions contribute minimally to the total of density of states. Besides, the calculations indicate that

2

AgVO3 holds a narrow bandgap of 1.65eV. The state density analysis illustrates that the

3

conduction band of AgVO3 primarily comes from V 3d orbit and the valence band principally

4

consists of Ag 4d and O 2p orbits (Figure 6d). Such a band alignment in the Ba5Ta4O15/AgVO3

5

system is of great importance in the boosting of photocatalytic performance.

6 7

Figure 6. The optimized geometric structure of (a) Ba5Ta4O15, (b) AgVO3. Calculated band

8

structures, DOS of (c) Ba5Ta4O15 and (d) AgVO3.


14

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1

Photocatalytic degradation of organic pollutant. The photocatalytic performances of the as-

2

prepared photocatalysts were evaluated by the frequently-used azo dye Acid Red G (ARG)

3

solution and typical antibiotic ciprofloxacin (CIP) under visible light irradiation. From Figure 7a,

4

the blank curves display that the ARG aqueous solution is stable under visible light irradiation.

5

Only 48% ARG in the solution were degraded for the pure AgVO3. A/BTO-3 sample exhibits the

6

highest photocatalytic activity, and the photocatalyst can degrade ARG by 90% after 2h. As

7

displayed in Figure S3, the peak at 505 nm rapidly weakened, indicating that the ARG molecular

8

was destructed by the Ba5Ta4O15/AgVO3 photocatalysts.35-37 Figure 7b displays the apparent rate

9

constants (h-1) of the Ba5Ta4O15, AgVO3, and A/BTO-1 to A/BTO-4. The results are 0.0142,

10

0.3176, 0.2649, 0.3618, 0.8388, 0.4504 h-1 respectively. From Figure 7c, it can be observed that

11

36, 50, 58, and 71% of CIP in the solution was degraded by Ba5Ta4O15/AgVO3 composites with

12

different content of Ba5Ta4O15. It is apparent that the A/BTO-3 composites displayed the highest

13

CIP degradation ability, which is similar to the photocatalytic degradation results of ARG. The

14

removal of TOC was chosen as a mineralization index to analyze the ARG degradation progress.

15

As shown in Figure 7d, the as-prepared A/BTO-3 composites obtained a total TOC removal

16

efficiency of 76 % after 3 h, which is higher than that of pure AgVO3 (42 %) under similar

17

conditions, indicating that the prepared Ba5Ta4O15/AgVO3 composites present enhanced

18

mineralization ability.


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Page 16 of 37

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Figure 7. (a) Photocatalytic degradation and (b) first-order rate constants of ARG solution over

3

the as-obtained composites. (c) Photocatalytic activity of the as-obtained compositesfor

4

degradation of CIP solution. (d) TOC removal curves of ARG degradation over AgVO3 and

5

A/BTO-3 photocatalysts.

6

To test the photostability of the Ba5Ta4O15/AgVO3 photocatalysts, the recycling capability of

7

the A/BTO-3 and AgVO3 was showed in Figure 8. It is demonstrated from Figure 8a that the

8

degradation ratio of pure AgVO3 decreased from 51% to 33% after four cycles. However, the

9

photocatalytic efficiency of the A/BTO-3 photocatalysts was effectively maintained even after

10

four cycles, which was only decreased from 81% to 74%. Compared with the bare AgVO3, the

11

existence of the Ba5Ta4O15 nanosheets supported the photocatalytic stability of the


16

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1

heterojunction composites. Moreover, the recovered A/BTO-3 after repeated experiments was

2

characterized by TEM, XPS and DRS. The TEM image (Figure 8b) exhibits that many small

3

particles are uniformly anchored on the surface of AgVO3 nanoribbons and the Ba5Ta4O15

4

nanosheets serve as the supports of loading Ag0 and AgVO3 in this heterojunction system. From

5

the HRTEM image of A/BTO-3 sample in Figure 8b, the interplanar distance of nanoparticles

6

loaded on the AgVO3 is 0.236 nm, which is in accordance with the (111) plane of Ag

7

nanopaticles. As illustrated in Figure 8c, the peaks at 367.6 and 373.9 eV were assigned to Ag+

8

of A/BTO-3. Where those at 368.5 and 374.5 eV were related to metallic Ag of AgVO3, the

9

generated trace amounts of Ag0 during preparation process mainly implied the photosensitivity

10

of AgVO3.38-39 Therefore, it is revealed that the metallic Ag nanoparticles could greatly influence

11

electronic structure in the photocatalytic system.40-43 UV–vis absorption spectra of original and

12

used A/BTO-3 sample are displayed in Figure 8d. Compared to the fresh A/BTO-3 sample, the

13

used A/BTO-3 sample exhibits broader absorption in the whole visible region, which should be

14

resulted from the SPR effect of the Ag nanoparticles deposited on the surface of the AgVO3. The

15

SPR effect could increase the separation efficiency of carriers on the photocatalyst

16

surface/interfaces, which could facilitate the generation of •O2-.9 These results indicate that Ag

17

nanoparticles was generated on the surface of the photocatalyst under photocatalytic progress,

18

which resulted in the enhanced light absorption and SPR effect for increased the photogenerated

19

carriers’ separation.


17


Page 18 of 37

1 2

Figure 8. (a) Cycle runs of the A/BTO-3 and AgVO3 for ARG degradation; (b) TEM and

3

HRTEM images of A/BTO-3 after 4 cycles used; (c) Ag 3d XPS spectra after 4 cycles use.

4

Possible photocatalytic mechanism. Radical species (h+, •O2- and •OH) trapping experiments

5

were measured to investigate the mechanism of the Ba5Ta4O15/AgVO3 photocatalysts for the

6

photocatalytic progress. Na2C2O4 (h+ scavenger), benzoquinone (•O2- scavenger) and isopropyl

7

alcohol (•OH quencher) were selected as scavengers during photocatalytic process. From Figure

8

9a, 90% of ARG in solution was degraded by the A/BTO-3 photocatalyst without any

9

scavengers. The degradation rate of ARG reduced to 17.8%, 51.3% and 66.2% with the existence

10

of Na2C2O4, BQ and IPA, respectively, which proves that both h+ and •O2- species and h+ species

11

were the major active species in the degradation process. In addition, ESR analyses were also


18

Page 19 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1

employed to explain the •OH and •O2- species in the Ba5Ta4O15/AgVO3 photocatalytic reaction

2

systems. No DMPO-•OH signals were measured in aqueous dispersions of A/BTO-3 composites

3

both in dark condition.52 The weak characteristic signals of DMPO-•OH were also recorded

4

when the irradiation time increased to 2 min, and then disappeared at 10 min. This reveals that

5

fewer •OH radicals were generated in the photocatalytic progress (Figure 9b). By reading Figure

6

9c, four obvious signals with A/BTO-3 composites were generated, which could be attached to

7

DMPO-•O2- under irradiation 10min. The generation of •O2- species in the photocatalytic

8

reactions can be demonstrated by the obtained ESR information, which further confirmed that

9

the SPR effect of Ag nanoparticles formed under light irradiation boosted the molecular oxygen

10

activation. Based on the above trapping experiments, a conclusion can be safely drawn that both

11

h+ and •O2- are crucial elements in the ARG degradation process while h+ is regarded as the

12

dominant active species.9

13 14

Figure 9. (a) Photocatalytic degradation of ARG solution over A/BTO-3 with the different

15

radical species scavengers; ESR of the (b) DMPO-•OH and (c) DMPO-•O2- for A/BTO-3 with

16

irradiation time of 2 and 10 min.


19


Page 20 of 37

1

To further analyse the improved photocatalytic activities of Ba5Ta4O15/AgVO3 composites in

2

detail, the PL spectroscopy of samples were conducted as follows. As shown in Figure 10a, the

3

AgVO3 exhibit a tough peak at around ~540 nm.19 However, when Ba5Ta4O15 nanosheets were

4

introduced, the intensity of this peak declined, suggesting that the recombination rate of carriers

5

was efficiently inhibited through the combination of AgVO3 and Ba5Ta4O15 nanosheets. This

6

process was then comprehended by the time-resolved transient PL analysis.44 For A/BTO-3, the

7

emission lifetimes of A/BTO-3 are longer than the corresponding lifetimes of AgVO3 as

8

exhibited in Figure 10b (τ1 = 0.912 ns, τ2 = 3.709 ns, and τ3 = 11.217 ns for A/BTO-3 versus τ1 =

9

1.122 ns, τ2 = 4.451 ns, and τ3 = 15.072 ns for AgVO3). The fluorescence lifetime of bare AgVO3

10

and A/BTO-3 heterojunction are 3.286 and 3.602 ns, respectively. Consequently, the

11

Ba5Ta4O15/AgVO3 composites displayed a longer lifetime compared with the pure AgVO3,

12

further illustrated that the photogenerated carriers have been efficiently separated in

13

heterojunction system, superior to those of bare AgVO3.45

14 15

Figure 10. (a) Photoluminescence spectra (PL) of AgVO3 and A/BTO-3; (b) Time-resolved

16

transient PL decay of AgVO3 and A/BTO-3.


20

Page 21 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1

In addition, the photocurrent of the Ba5Ta4O15, AgVO3 and A/BTO-3 were depicted in Figure

2

11a. The transient photocurrent collected by A/BTO-3 was much higher than those of AgVO3

3

and Ba5Ta4O15 under Xe lamp irradiation，which illustrated that the collaborative effects of the

4

interface of AgVO3 and Ba5Ta4O15 in this heterojunction system could generate more charge

5

carriers. The Electrochemical impedance spectroscopy (EIS) could be taken as an available

6

strategy to explain the charge transfer efficiency.9 Typically, a lower arc in the EIS plot evinced

7

a slenderer charge-transfer resistance. It is observed that the plots for the as-obtained samples

8

were presented in the following sequence: A/BTO-3 < AgVO3 ≤ Ba5Ta4O15, indicating that the

9

A/BTO-3 sample held the lowest resistance (Figure 11b). The unique property made the A/BTO-

10

3 sample presenting higher faster interfacial charge transfer and higher carriers ‘separation

11

efficiency, which is similar to the results of PL, transient photoluminescence and PT tests.46

12 13

Figure 11. (a) Transient photocurrent and (b) electrochemical impedance spectroscopy (EIS)

14

spectra of the Ba5Ta4O15, AgVO3 and A/BTO-3 under Xe lamp irradiation.

15

A possible mechanism for degradation of ARG solution on the Ba5Ta4O15/AgVO3 composite

16

is illustrated in Figure 12. The valance band positions of Ba5Ta4O15 and AgVO3 were determined

17

by the VB-XPS spectrum in Figure S4. Considering the band gaps of the Ba5Ta4O15 and AgVO3,


21


Page 22 of 37

1

the VB and CB of Ba5Ta4O15 and AgVO3 were calculated to be 1.80/-2.00 eV and 2.25/0.30 eV

2

respectively. For heterojunction photocatalysts, a suitable matching of their CB and VB positions

3

can boost the photogenerated charge carriers transfer from one to another, which can contribute

4

to improving the photocatalytic performances.47-50 As a result of the appropriate band gaps,

5

AgVO3 could be excited under visible light to generate photoinduced electrons and holes. As the

6

VB of AgVO3 (2.25 eV) is more positive than that of Ba5Ta4O15 (1.80 eV), the photoinduced

7

holes will transfer from the VB of AgVO3 to the VB of Ba5Ta4O15. The holes (h+) can partly

8

oxidize the adsorbed H2O molecules in solution to •OH radicals owing to the potential for h+ is

9

higher than •OH (+1.99 eV vs NHE). Meanwhile, rich holes left on the VB of Ba5Ta4O15 have

10

powerful potential to oxidize ARG directly. In addition, the inner spontaneous polarization

11

potential of Ba5Ta4O15 nanosheets can be applied to provide a build-in electric field. As a typical

12

perovskite ferroelectric material, when Ba5Ta4O15 nanosheets contacts with another

13

semiconductor like AgVO3, the self-polarization could induce free carriers’ redistribution in

14

another semiconductor, which is similar to Ag2O/BaTiO3 photocatalyst.51 It is worthy of noting

15

that it is much beneficial for carriers transfer to introduce Ba5Ta4O15 nanosheets on the surfaces

16

of AgVO3 by capturing holes.20 The interaction of Ba5Ta4O15 and AgVO3 accelerated the

17

separation and transfer efficiency of photogenerated carriers, and then further enhancing the

18

photocatalytic activity. Remarkably, it is in great agreement with the results of the

19

photoelectrochemical analysis. At the same time, the electrons in the CB of AgVO3 would move

20

quickly to Ag nanoparticles owing to the high conductivity of the Ag nanoparticles, which could

21

help the decrease of the recombination probability of carriers.52-55 The electrons in CB of AgVO3

22

(+0.3 eV) are not enough to reduce O2 to •O2- (-0.33 eV vs NHE). Nevertheless, the electrons

23

would escape from the AgVO3, which decreases the reduction of Ag+, resulting in stable charge


22

Page 23 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1

transfer path. The electrons transferred from AgVO3 could be trapped by molecular oxygen to

2

form reactive oxygen species(•O2-), which is similar to that of other silver-based

3

photocatalysts.56-59 Produced by the mutual oscillations of Ag surface electrons, the SPR effect

4

could give rise to the local inner electromagnetic field.60 Under the influence of local

5

electromagnetic field, the electrons and holes that generated on the surface of AgVO3 could also

6

be effectively separated.55 For another, Ag nanoparticles loaded on AgVO3 nanoribbons could

7

play an important role as electron traps, hence accelerating the separation of photogenerated

8

carriers and enhancing interfacial electron transfer. The heterojunction formed between the

9

AgVO3 and Ba5Ta4O15 significantly enhances the separation efficiency of the photo-induced

10

carriers and advances the photocatalytic performance of the Ba5Ta4O15/AgVO3 composite.61

11 12

Figure 12. Photocatalytic mechanism for Ba5Ta4O15/AgVO3 composite under visible light

13

irradiation.


23


Page 24 of 37

1

Conclusion

2

Heterojunction photocatalysts of Ba5Ta4O15/AgVO3 has been successfully synthesized by a facile

3

two-step self-assembly strategy. After the introduction of Ba5Ta4O15 nanosheets, the

4

heterojunction photocatalysts exhibited excellent photocatalytic oxidation activity as compared

5

to pure Ba5Ta4O15 and AgVO3 under visible light irradiation. It can be verified by all trapping

6

experiments that h+ and •O2- were the principal active radical species for pollutants degradation.

7

The enhanced photocatalytic activity of Ba5Ta4O15/AgVO3 could correspond to the holes

8

dominated charge transfer progress and localized surface plasmon resonance (LSPR) leading to

9

the suppressed recombination of photogenerated electron–hole pairs. This work demonstrates

10

that Ba5Ta4O15/AgVO3 photocatalysts could be recognized as a potential high efficient

11

photocatalyst for environmental pollutant removal.

12

Supporting Information

13

Figures showing the EDX mapping, BET analysis, UV–vis absorption spectra and VB-XPS of

14

samples.

15

AUTHOR INFORMATION

16

Corresponding Author

17 18 19 20

*Phone, fax: +86-27-87887445. E-mails: [email protected] Notes The authors declare no competing financial interest. Acknowledgments


24

Page 25 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1

The study was supported by the National Natural Science Foundation of China (NSFC

2

No.51472194 and No.51602237), the NSF of Hubei Province (2016CFA078) and the National

3

Basic Research Program of China (973 Program No.2013CB632402).

4 5


25


1

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Table of Contents (TOC) Graphic

1

2 3

Synopsis:

4

Synergistic effect of heterostructure and plasmon resonance facilitated the separation efficiency

5

of carriers for organic pollutant degradation.


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AgVO3 Nanoribbon Heterojunctions with

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