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Thylakoid-Inspired Multi-Shell g-C3N4 Nanocapsules with Enhanced Visible-Light Harvesting and Electron Transfer Properties for High-Efficiency Photocatalysis Zhenwei Tong, Dong Yang, Zhen Li, Yanhu Nan, Fei Ding, Yichun Shen, and Zhongyi Jiang ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.6b08251 • Publication Date (Web): 29 Dec 2016 Downloaded from http://pubs.acs.org on December 30, 2016

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Thylakoid-Inspired Multi-Shell g-C3N4 Nanocapsules with Enhanced Visible-Light Harvesting and Electron Transfer Properties for High-Efficiency Photocatalysis Zhenwei Tong a,d, Dong Yang b,c, Zhen, Li a,d, Yanhu Nan a,d, Fei Ding a,d, Yichun Shen a,d, Zhongyi Jiang*a,d a

Key Laboratory for Green Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China. b Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 30072, China c School of Environmental Science and Engineering, Tianjin University, 300072 Tianjin, China d Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China Corresponding author: Zhongyi Jiang, E−mail: [email protected]

ABSTRACT: Inspired by the orderly stacked nanostructure and highly integrated function of thylakoids in natural photosynthesis system, multi-shell g-C3N4 (MSCN) nanocapsule photocatalysts have been prepared by SiO2 hard template with the different shell layers. The resultant triple-shell g-C3N4 (TSCN) nanocapsules display superior photocatalysis performance to the single-shell and double-shell counterparts owing to the excellent visible-light harvesting and electron transfer properties. Specially, with the increase of the shell layer number, the light harvesting is greatly enhanced: the increase of the entire visible range absorption arisen from the multiple scattering and reflection of the incident light within multi-shell nano-architectures as well as the light transmission within the porous thin shells; the increase of absorption edge arisen from the decreased quantum size effect. The electron transfer is greatly accelerated by the mesopores in thin shells as nanoconduits and the high specific surface area of TSCN (310.7 m2 g−1). With the tailored hierarchical nanostructure features, TSCN exhibits a superior visible-light H2-generation activity of 630 µmol h-1 1

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g-1 (λ>420 nm), which is among one of the most efficient metal-free g-C3N4 photocatalysts. This study demonstrates a bioinspired approach to the rational design of high-performance nanostructured visible-light photocatalysts. KEYWORDS:

g-C3N4,

multi-shell

nanocapsules,

harvesting, photocatalysis

2


thylakoids,

visible-light

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Visible-light photocatalysis, as core technology of solar energy conversion, has been explored for nearly half a century and exhibits fascinating application prospects in energy and environment relevant areas.1-4 Among the numerous existing photocatalysts, graphitic carbon nitride (g-C3N4), as a metal-free semiconductor, has drawn ever booming attentions owing to its desirable visible-light response (λ420 nm), arising from its limited visible-light absorption, poor charge transport capability and low specific surface area; whilst these g-C3N4 nanocapsules exhibit an apparent enhancement in the H2-generation rate (13.7, 20.1, and 25.2 µmol h-1 for SSCN, DSCN and TSCN, respectively), primarily attributing to the increased visible-light utilization, low electron–hole recombination and high specific surface area. The excellent H2-generation performance of TSCN reveals one of the highest H2 production rate in the reported g-C3N4 photocatalysts.11,44,45 In addition, the photocatalytic degradation of dye was also measured under visible light irradiation (λ>420 nm). As presented in Figure 5b, nearly no RhB was photodegraded in the absence of photocatalyst. Bulk CN only degrades nearly 35% RhB within 80 min irradiation; while SSCN, DSCN and TSCN nanocapsules all exhibit much higher RhB degradation capacity than bulk CN. TSCN is able to completely degrade RhB within 80 min irradiation, which is much higher than SSCN and DSCN, even higher than the reported mesoporous g-C3N4 materials and g-C3N4 nanosheets.46,47 The RhB degradation over g-C3N4 samples obeys the first-order kinetics, i.e. ln(C0/C) = kt, where C0 and C are the concentration at the time zero and the concentration at time t for RhB, k is the degradation reaction rate constant, respectively. The k value of 14


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TSCN is 1.459 h−1, which is about 2.5, 1.5 and 6.0 times higher than that of SSCN, DSCN and bulk CN, respectively (Figure S5a). This greatly elevated degradation capability of MSCN nanocapsules can be maintained within five-cycle photocatalytic reactions (Figure 5c). The absorption peak gradually shifts from 553 to 498 nm and its intensity gets weaker over time, further indicating the degradation of RhB (Figure S5b).48 The trapping experiments shows that h+ is the major reactive species involved in the RhB degradation over TSCN (inset of Figure S5b). Meanwhile, MSCN preserves the whole nanocapsule structure without collapse after the long-time reaction (Figure S1e), indicating its promising practical application. The mesoporous structure of MSCN affects the reaction kinetics. The adsorption capacity of TSCN could reach 38% after adsorption equilibrium, while only 17% and 8% for the SSCN and bulk CN, respectively. Accordingly, it was found that the multiple-shell structure does not inhibit the mass transfer (compared with SSCN) but increase the kinetic response due to its large specific surface area (115.2, 209.5 and 310.7 m2 g−1 for SSCN, DSCN and TSCN, respectively) and porous channels. To further verify the positive effects of multi-shell structure in light harvesting, we destroyed the three shells of MSCN by mechanical milling and strong sonication, and evaluated its photocatalytic performance. Upon shattering, the photocatalyst still preserved mesopores but the multi-shell morphology was broken. Without light penetration and reflection, a 36% decrease appeared in degradation activity (Figure S5c) just as expected. In addition, TGA in moisture loss stage suggests that the mass loss of MSCN is more pronounced than that of bulk CN under the identical thermal treatment condition and uniform pretreatment (see the supporting information in Figure S5d), which demonstrated that MSCN has better water-retention capacity due to its nanocapsule structure. Scheme 2. Schematic diagram showing the photocatalytic reaction over MSCN photocatalyst under visible light irradiation.

15


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Based on the above analysis, the photocatalytic mechanism of MSCN is proposed, as shown in Scheme 2. It is well known that common heterogeneous photocatalysis often contains the following four steps: (i) light harvesting; (ii) photoexcitation to generate charge carriers; (iii) charge separation and transfer to surface of catalyst and recombination thereby; (iv) surface adsorption as well as redox reaction.9 These four steps are significantly influenced by the intrinsic features of photocatalysts, including bandgap, composition and morphology, an integration of these characteristics would optimize the above four steps, acquiring a maximum enhancement of catalytic activity. MSCN synthesized here presents such a successful example. First, both the morphology and electronic structure of MSCN have been manipulated to utilize more incident light. The electrons in VB of g-C3N4 can be migrated to the CB by visible light excitation, keeping the photogenerated holes in VB. The multiple mesoporous shells and cavities of MSCN allow the multiple reflections and scattering of light within the interiors of cavities as well as inside their pore channels, thus enhancing light harvesting and offering more photogenerated electrons and holes. Second, the hierarchical morphology of MSCN can facilitate the photo-generated electrons and holes transfer. In detail, photogenerated charge carriers in bulk of MSCN can quickly migrate to its surface along interplanar direction, because of the small thickness of shells, or transfer to the wall of mesopores in shell; whereas the charge carriers on the surface can readily migrate to the reaction sites along in-plane direction. Third, features including large accessible surface area, good permeability, and high water-retention capacity can not only supply plentiful catalytic active centers, but also 16


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improve adsorption and diffusion process during the reaction. At last, H2O or dye molecules will experience the redox reactions around the catalytic center, generating H2 or being degraded. CONCLUSIONS In summary, inspired by the orderly stacked nanostructure and the highly integrated functionalities of thylakoids in natural photosynthesis system, multi-shell g-C3N4 nanocapsules were synthesized by a facile and controllable templating method for high-efficiency visible-light photocatalysis. The tailored nanostructure of resultant MSCN, which encompasses the multiple shells, hollow cavities and mesopores in thin shells, is highly favorable for visible-light harvesting and electron transfer with long lifetimes. Accordingly, the triple-shell g-C3N4 nanocapsules exhibit superior photocatalytic performance to single-shell, double-shell g-C3N4 nanocapsules, which can produce H2 as high as 630 µmol h-1 g-1 and completely degrade dye within 80 min under visible light. Our bioinspired strategy may represent a significant advance in developing high-efficiency and cost-effective visible-light photocatalysts for solar energy conversion. EXPERIMENT SECTION Materials Cyanamide

(98%), tetraethyl

2-bis(triethoxysilyl)ethane

orthosilicate (TEOS),

(BTSE)

were

bought

Triton

from

X-100

Tianjin

and 1,

Xiensi

Ltd.

Cetyltrimethyl ammonium bromide (CTAB), HCl (37%), ethanol, ammonia aqueous solution (30%) were purchased from Tianjin Kewei Ltd. All chemical regents were of analytical grade. Synthesis of Multi-Shell SiO2 Nanospheres Multi-shell SiO2 nanospheres were obtained by a sol-gel method according to a modified previously described procedure.23 Typically, CTAB (0.08 g) was added in a mixture (53 ml) of concentrated ammonia (30 wt%), water and ethanol (at a volume ratio of 1:75:30). After stirring for one hour at 35 °C, BTSE (0.125 mL) and TEOS (0.125 mL) were mixed at first and then quickly dissolved in the solution under 17


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drastic stirring (1100 rpm) for 24 h. Then a mixed solution of BTSE and TEOS was quickly added again under the same condition, keeping stirring for another 24 h. Next, the mixed solution was quickly added into the solution the third time, keeping stirring for another 24 h. Afterward, the procured ethane-bridge organosilica spheres were gathered, re-dispersed in 720 mL of water and heated for 5 h at 120 °C to accomplish the multi-interface conversion. The product was collected and subsequently CTAB in the product was gotten rid of by the solvent-extraction process. Finally, triple-shell hollow SiO2 nanospheres were acquired after ethanol washing and vacuum drying. The single- and double-shell SiO2 nanospheres were also synthesized via one batch and two batches addition of the mixture of BTSE and TEOS following the above procedure, respectively. Synthesis of MSCN Nanocapsules After annealed at 600 oC for 2 h in air atmosphere, the obtained multi-shell SiO2 nanosphere (0.1 g) was mixed with 2 g cyanamide and together poured into deionized water (5 mL), keeping stirring at 40 oC for 8 h. Next, the mixed solution was centrifuged, freezing-dried and heated to 550 oC for 3 h under N2 protective flow of 50 mL min-1. The resulting powder was treated with Na2CO3 solution (0.3 mol L-1, 20 mL) at 60 oC for 24 h to remove SiO2 template. Finally, the multi-shell g-C3N4 nanocapsules were obtained. Characterization Most of instruments used in this manuscript are identical to that in our recent work, and the detailed information has been described in the related reference.49 High resolution transmission (HRTEM) and high angle annular dark field (HADDF) were conducted at 90 K using a JEOL-2011. Scanning electron microscopy (SEM) was performed on an FEI Nova XL430 instrument. X-ray diffractometer was operated on a Rigaku D/max 2500V/PC instrument. Fourier transform infrared spectroscopies (FTIR) were recorded by a Nicolet-560 spectrometer. X-ray photoelectron spectroscopy (XPS) was performed on a Perkin-Elmer PHI 1600 ESCA instrument. The diffuse reflectance spectra were conducted using UV-vis spectrophotometer 18


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(U-3010, Hitachi). Photocurrent performance was performed on a BAS Epsilon Electrochemical System. The characterization of resonant light scattering (RLS) spectra: 5 mL 0.05% (v/v) Triton X-100 was firstly mixed with 50 mL absolute ethanol, and then 20 mg MSCN samples were added into the solution. After ultrasound for 30 min, the obtained mixture was tested by a spectrofluorimeter (Hitachi, F-4600). After synchronizing excitation and emission, the RLS spectra were conducted with the wavelength range of 200-800 nm and 2.5 nm slit width. The RLS intensity, ∆IRLS=IRLS-I0RLS, in which

IRLS and I0RLS are the magnitudes of the solution with and without photocatalyst. Photoelectrochemical Measurements Photoelectrochemical performance of samples was tested using a standard three-electrode system with Pt filament as a counter electrode, Ag/AgCl as a reference electrode and Na2SO4 (0.5 mol L-1) as the electrolyte solution. For preparing a working electrode, an F-doped SnO2 (FTO) glass (0.8 × 0.8 cm2) was coated by multi-shell g-C3N4 nanocapsules slurry. Specifically, the slurry was dipped (3 drops) and spin-coated (2000 r min-1, 30 s) onto an FTO glass, and then dried at 40 °C for next coating. This coating process was repeated 5 times. Subsequently, the coated FTO glass was calcined at 300 °C for one hour. Total working electrodes of MSCN nanocapsules were prepared using above process with the same concentration, coating times and coating area, thus leading to a similar loading weight of catalyst (1.151, 1.118, 1.130 and 1.125 mg for bulk CN, SSCN, DSCN and TSCN electrode, respectively). The photocurrent and Mott-Schottky spectroscopy were measured by using VERASTA2273 analyzer. The photocurrent was recorded with AM 1.5 (100 W cm-2) simulated sunlight irradiation. Photocatalytic Activity The experiments on hydrogen evolution from the water splitting were carried out under visible light at room temperature. Specifically, 40 mg photocatalyst was suspended in a mixture of 10 mL triethanolamine (TEOA, as sacrificial reagent) and 80 mL water under stirring. 3 wt% Pt was in-situ photoreduced onto the catalyst 19


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surface during the reaction. The suspension was bubbled with argon gas for half an hour to remove air and then sealed, which has been described detailedly in our recent work.49 A Xe lamp (300 W) with a cutoff filter (λ>420 nm) was employed to irradiate the sealed tube. In time of reaction, 0.2 ml gas evolution was sampled every hour and analyzed with Shimadzu GC gas chromatography. To get an accurate amount of the generated H2, an average value from 3 times’ measurement was adopted. Photodegradation of RhB (10 mg L–1) was carried out using a Xe lamp with a 420 nm cutoff filter (500 W, 10 mW cm–2). The reaction suspension consists of 30 mL RhB solution and 30 mg photocatalyst. Before illumination, this suspension was stirred in the dark to guarantee that the adsorption-desorption equilibrium was reached. 2.0 mL suspension

was

sampled

in

every

irradiation

interval.

Then,

a

UV-vis

spectrophotometer (Hitachi, U-3010) was used to analyze RhB concentration at its maximal absorption wavelength (553 nm). ACKNOWLEDGMENTS The authors thank the financial support from the National Science Fund for Distinguished Young Scholars (21125627), National Natural Science Fund of China (21406163, 91534126, 21621004), Tianjin Research Program of Application Foundation and Advanced Technology (15JCQNJC10000), Program of Introducing Talents of Discipline to Universities (B06006). SUPPORTING INFORMATION AVAILABLE The additional experimental data including the TEM images, XRD and FTIR spectra of SSCN and DSCN, the kinetic curves of RhB degradation, the TG curves TSCN and bulk CN, the RLS spectra. This materials is available free of charge via the Internet at http://pubs.acs.org. REFERENCES 1. Ong, W. J.; Tan, L. L.; Ng, Y. H.; Yong, S. T.; Chai, S. P. Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer to Achieving Sustainability? Chem. Rev. 2016,

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Inspired by the delicate stacked structure of thylakoids in natural photosynthesis system, multi-shell g-C3N4 nanocapsules are designed and prepared, which displays the superior visible-light photocatalytic performance due to the increases in incident light harvesting and electron transfer flexibility. (300×300 dpi)

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Thylakoid-Inspired Multishell gC - ACS Publications - American

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