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Research Article www.acsami.org Imparting Catalytic Activity to a Covalent Organic Framework Material by Nanoparticle
Research Article

Research Article

Imparting Catalytic Activity to a Covalent Organic Framework Material by Nanoparticle Encapsulation

Xiaofei Shi, Youjin Yao, Yulong Xu, Kun Liu, Guangshan Zhu, * , § Lifeng Chi, * , and Guang Lu* ,

§ Lifeng Chi, * , † and Guang Lu * , † † Institute of Functional
§ Lifeng Chi, * , † and Guang Lu * , † † Institute of Functional

Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China § Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China

* S

Supporting Information

ABSTRACT: Integrating covalent organic frameworks (COFs) with other functional materials is a useful route to

ABSTRACT: Integrating covalent organic frameworks (COFs) with other functional materials is a useful route to enhancing their performances and extending their applications. We report herein a simple encapsulation method for incorporating catalytically active Au nanoparticles with di er- ent sizes, shapes, and contents in a two-dimensional (2D) COF material constructed by condensing 1,3,5-tris(4-amino- phenyl)benzene (TAPB) with 2,5-dimethoxyterephthaldehyde (DMTP). The encapsulation is assisted by the surface functionalization of Au nanoparticles with polyvinyl- pyrrolidone (PVP) and follows a mechanism based on the adsorption of nanoparticles onto surfaces of the initially formed polymeric precursor of COF. The incorporation of nanoparticles does not alter obviously the crystallinity, thermal stability, and pore structures of the framework matrices. The obtained COF composites with embedded but accessible Au nanoparticles possess large surface areas and highly open mesopores and display recyclable catalytic performance for reduction of 4-nitrophenol, which cannot be catalyzed by the pure COF material, with activities relevant to contents and geometric structures of the incorporated nanoparticles. KEYWORDS: covalent organic framework, porous materials, nanoparticles, catalysis, composites

incorporated nanoparticles. KEYWORDS: covalent organic framework, porous materials, nanoparticles, catalysis, composites

INTRODUCTION

Covalent organic frameworks (COFs) are a new class of porous crystalline materials constructed by organic building blocks via covalent bonds. 1 8 The molecular engineering-based synthesis strategy of COFs allows the exible design for achieving unique structures and properties. Their two-dimensional (2D) or three-dimensional (3D) open network structures yield high surface areas and accessible cavities or channels with uniform sizes ranging from angstroms to nanometers, which is attractive for many applications including gas storage, 9 13 separa- tions, 14 16 drug delivery, 17 19 and energy conversion and storage. 20 23 Built with functional moieties, COF materials can be endowed with unique optical, 24 28 optoelectronic, 29 31 and catalytic properties. 32 34 Alternately, noninherent functional- ities and extended applications of COFs can be achieved by reasonably integrating them with other functional materials. The open porous structures and outstanding stability of COFs make them excellent host matrices for many functional species such as proton carriers, 35 37 electron acceptors, 38 40 and enzymes. 41 The cavities themselves of COF materials have also been explored as nanoreactors for chemical reactions. Based on the conned synthesis , metal nanoparticles can be

con fi ned synthesis ” , metal nanoparticles can be © XXXX American Chemical Society A

© XXXX American Chemical Society

A

produced within the cavities of COFs with ultrasmall sizes and clean surfaces . 42 46 New and enhanced performances that are relevant to the nanoparticle components have been observed for the obtained nanoparticles/COF composites in organic catalysis 42 45 and hydrogen storage applications. 46 Alternately, this kind of composite can be generated by encapsulating the preprepared nanoparticles during the framework synthesis. This strategy is attractive since the compositions, sizes, and shapes associated with the chemical and physical properties of nanoparticles can be feasibly tuned by their well-established synthesis. 47 , 48 COF materials can heterogeneously nucleate and grow around the outer surfaces of some nanosized objects (e.g., carbon nanotubes with diameter of 50 nm, 49 ZnO nanorods with diameter of 100 nm, 50 and 200 nm Fe 3 O 4 spheres 51 ) to give the coreshell structures, just as they did on the surface of a at substrate. 52 54 Nevertheless, although the encapsula- tion strategy, in principle, is capable of incorporating any nanoparticles with the desired chemical or physical properties

Received: December 19, 2016 Accepted: February 6, 2017

DOI: 10.1021/acsami.6b16267 ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX

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Scheme 1. Schematic Illustration of the Encapsulation of PVP-Modi ed Nanoparticles in the 2D TAPB-DMTP-COF

of PVP-Modi fi ed Nanoparticles in the 2D TAPB-DMTP-COF in COF materials, the nanoparticle-relevant catalysis

in COF materials, the nanoparticle-relevant catalysis applica- tions of the resulting COF composites have not been reported yet. For 2D COF-based composites, the orientation of channels and possible crystal defects (e.g., amorphous portion and stacking faults) in the framework matrices may also raise doubts about the accessibility and catalytic activity of the enshrouded nanoparticles. In addition, for the systematic investigation on the catalytic performance of the resulting composites, it is highly desirable to develop new encapsulation methods that enable the easy incorporation of smaller nanoparticles (<50 nm) (and even multiple types of nanoparticles) within COFs with tunable contents. In this study, we report a general encapsulation method for incorporating nanoparticles with di erent sizes and shapes in a 2D COF material ( Scheme 1). This strategy involves the optimization of framework synthesis and the surface function- alization of nanoparticles. The highly crystalline 2D TAPB- DMTP-COF, we chose in this work, has been reported previously and displays outstanding chemical robustness and thermal stability. 33 Au nanoparticles were chosen as examples to demonstrate our encapsulation method due to their easy synthesis and excellent catalytic activities for many chemical reactions. 55 The surfaces of nanoparticles used in our work were functionalized with polyvinylpyrrolidone (PVP), an amphiphilic surfactant, that has been widely used for controlling the sizes, shapes, and surface properties of a variety of nanoparticles. 56 58 Relying on the adsorption of PVP- modied nanoparticles onto the initially formed polymeric precursor of COF, instead of the heterogeneous nucleation reported previously for the formation of coreshell-structured composites, 49 51 nanoparticles with sizes ranging from 3.8 to 100 nm and with shapes in sphere and rod can be incorporated with high e ciency in TAPB-DMTP-COF during its synthesis

under the optimized experimental conditions. The composites display high crystallinity, excellent thermal stability, large surface areas, and open mesopores that are substantially similar to those of the pure TAPB-DMTP-COF. In the model reaction of 4-nitrophenol reduction by NaBH 4 , 43 , 59 61 the composites containing Au nanoparticles show recyclable catalytic capability, but the pure COF material does not, establishing the accessibility and activity of the encapsulated nanoparticles within the 2D COF. In addition, systematic investigation with samples incorporated with di erent Au nanoparticles reveals the nanoparticle-relevant catalytic performances of the composites, where higher activity (with rate constants of 0.46 and 0.36 min 1 ) was observed for samples containing 15 nm Au nanoparticles (0.20 and 0.10 wt %), moderate activity (with rate constant of 0.36 min 1 ) for that containing 25 × 100 nm Au nanorods (0.26 wt %), and lower activity (with rate constant of 0.12 min 1 ) for that containing 50 nm Au nanoparticles (0.38 wt %).

EXPERIMENTAL SECTION

General Procedure of Nanoparticle Encapsulation in TAPB- DMTP-COF. A 20 mL borosilicate glass vial was charged with 1,3,5- tris(4-aminophenyl)benzene (TAPB) (0.030 mmol, 10.5 mg), 2,5- dimethoxyterephaldehyde (DMTP) (0.045 mmol, 8.7 mg), 4 mL of 1,4-dioxane butanol (v/v, 1:1), 0.5 mL of solution of PVP-modi ed nanoparticles in methanol, and 0.05 mL of 12 M aqueous acetic acid. The mixture was allowed to react at room temperature for 2 h. After adding 0.45 mL of 12 M aqueous acetic acid, the reaction was conducted further at 70 °C for 24 h. After cooling to room temperature, the product was collected by centrifugation, washed several times with tetrahydrofuran (THF) and acetone, and vacuum- dried at room temperature overnight. Other experiment and characterization details are provided in the Supporting Information .

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DOI: 10.1021/acsami.6b16267 ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX

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RESULTS AND DISCUSSION

Nanoparticles were synthesized using established methods, and their surfaces were functionalized with PVP during or after their synthesis (see experimental details in the Supporting Information ). The PVP-modi ed nanoparticles can be dispersed well in common polar solvents (for example, water and methanol) and are also stable in a mixture of methanol/ butanol/1,4-dioxane (v/v/v, 1:4:4), which was optimized as solvents for the synthesis of COF material in our experiment. The encapsulation process was demonstrated with 15 nm Au nanoparticles. Typically, a homogeneous solution containing PVP-modi ed Au nanoparticles, 1,3,5-tris(4-aminophenyl)- benzene (TAPB), and 2,5-dim ethoxyterephthaldehyde (DMTP) in methanol/butanol/1,4-dioxane was prepared, and acetic acid aqueous solution was subsequently introduced to trigger the condensation reaction between amino and aldehyde monomers. The mixture was allowed to react at room temperature for 2 h and then at 70 ° C for 24 h. The product collected by centrifugation displays homogeneous color (yellow), and the supernatant is transparent and absent of the discernible UV vis absorption peak at 520 nm (characteristic for 15 nm Au nanoparticles) ( Figure S2), implying that essentially a ll of the nanoparticles are incorporated in the product. Scanning electron microscope (SEM) images show that the product consists of spheres with an average diameter of 1.03 μ m ( Figure 1 a). These spheres

diameter of 1.03 μ m ( Figure 1 a). These spheres Figure 1. Microscopy characterizations of

Figure 1. Microscopy characterizations of COF composite containing 0.20 wt % 15 nm Au nanoparticles: (a) low-magni cation SEM image, (b) high-magni cation SEM image, (c) low-resolution TEM image, and (d) high-resolution TEM image.

exhibit rough surfaces on which convex domains with sizes of 50100 nm could be observed clearly ( Figure 1b). Trans- mission electron microscopy (TEM) measurements reveal that each (brighter) polymer sphere contains either single or several (darker) Au nanoparticles in their central regions ( Figure 1c). Essentially, no unencapsulated nanoparticles were observed outside the spheres or on their outer surfaces. Close observation at the edges of spheres under higher magnication

C

indicates that the spheres consist of domains that contain regular channels arranged along the radial direction of spheres ( Figure 1 d). The grain sizes of domains are about 50 nm along the orthogonal direction of channels, in consistent with that of the convex domains observed in SEM. Previous studies on the morphology evolution of the 2D Dha-Tab-COF have showed that the ππ stacking of 2D COF layers along the c -axis can result in the formation of rod-like crystallites possessing the hexagonally arrayed channels, which can self-assemble further and evolve to form dense or hollow COF spheres. 41 We speculate that, similarly, the spheres in current work are presumably aggregates of the rod-like crystallites. However, more TEM investigation on the possible ordered structures within bodies of spheres was frustrated by the large sizes of spheres and the overlapping projections of channels. High nanoparticle-encapsulation eciency (>99%) could be achieved for polymer spheres using the current method. The contents of nanoparticles can be tuned by changing the concentration of nanoparticles in the stock solutions ( Table S1 ). The fraction of polymer spheres containing single Au nanoparticle in the products was observed to increase as lowering the concentration of nanoparticles used in the synthesis, however, at the expense of a slight decrease in the encapsulation eciency ( Figure S3 ). The nal sizes of polymer spheres do not change obviously on tuning nanoparticle concentrations or even in the absence of nanoparticles in the synthesis, suggesting that the presence of nanoparticles does not alter substantially the homogeneous nucleation and subsequent growth of polymer spheres under current synthetic conditions. The encapsulation process was further investigated by time-dependent TEM analysis ( Figure S4). The adsorption of Au nanoparticles onto surfaces of the gradually formed oligomeric polymer precursors (with irregular shapes), instead of the nanoparticle@polymer core shell morphology, was observed commonly in the early time ( 15 min) of the encapsulation process (Figure S4b ). The above results suggest that the encapsulation of nanoparticles does not follow predominantly the heterogeneous nucleation mechanism. We speculate that in the current solution system the hydrophilic/ hydrophobic interactions between PVP molecules adsorbed on the nanoparticle surfaces and the initially formed tiny oligomeric polymer precursors (with high surface energy) are responsible for the adsorption of nanoparticles on the surfaces of polymeric precursor of COF, resulting in the nal encapsulation of nanoparticles as polymer spheres subsequently growing. In fact, the PVP-assisted encapsulation strategy has been adopted previously for incorporating nanoparticles in other materials such as silica 62 and metalorganic frameworks (MOFs) 63 based on either heterogeneous nucleation or nanoparticle adsorption. In an additional control experiment with excess free PVP intentionally added in the reaction, severe agglomeration of polymer spheres was observed in the product ( Figure S5), suggesting again the strong interactions between PVP and polymer of spheres. In principle, this encapsulation method is applicable to any nanoparticles that are chemically stable in the acidic solution system used in current work since the surface modication with PVP is easy to operate and has proved to work well for various nanoparticles di ered in compositions, sizes, and shapes. In fact, composites containing 50 nm Au nanoparticles, 25 × 100 nm Au nanorods, and 3.8 nm Pt nanoparticles were also successfully prepared using this method ( Figure 2a c). The agglomeration of polymer spheres observed in the Pt

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ACS Applied Materials & Interfaces Research Article Figure 2. TEM images of COF composites containing (a)

Figure 2. TEM images of COF composites containing (a) 0.38 wt % 50 nm Au nanoparticles, (b) 0.26 wt % 25 × 100 nm Au nanorods, (c) 3.8 nm Pt nanoparticles, and (d) 15 and 50 nm Au nanoparticles.

nanoparticle-containing product is presumably due to the existence of a small amount of free PVP in the nanoparticle stock solution even after intensive washing process. In addition, the simultaneous encapsulation of di erent types of nano- particles within the composites can also be achieved easily. Although we just demonstrated this exibility using 15 and 50 nm Au nanoparticles ( Figure 2 d), multifunctional composites could be prepared by encapsulating more than one types of nanoparticles with judicious selection. The crystallinity of the obtained composites was investigated by powder X-ray di raction (XRD) measurements. As shown in Figure 3 and Figure S7 , all the samples display an intense peak at 2.79 °, moderate peaks at 4.84 ° , 5.60° , and 7.39 ° , and weak peaks at 9.73 ° and 25.42 ° in their di raction patterns, which is

and 25.42 ° in their di ff raction patterns, which is Figure 3. Powder XRD patterns

Figure 3. Powder XRD patterns for as-synthesized COF and COF composite containing of 0.20 wt % 15 nm Au nanoparticles and simulated XRD pattern for TAPB-DMTP-COF. Inset is the same XRD pattern for the Au/COF composite but with the adjusted intensity scale, where weak peaks associated with di raction of COF can be observed but those assignable to Au nanoparticles cannot.

D

consistent with that of TA PB-DMTP-COF previously reported, 33 suggesting that the TAPB-DMTP-COF materials synthesized using current protocol are highly crystalline and that the incorporation of nanoparticles does not degrade obviously the crystallinity of framework matrices. The di raction peaks assignable to nanoparticles are too weak to be observed clearly in the patterns of hybrid composites presumably due to their low contents (and small sizes). However, energy-dispersive X-ray microanalysis (EDX) (Figure S9 ) and inductively coupled plasma analysis (ICP) con rm explicitly their existence in the composites. Thermogravimetric analysis (TGA) ( Figure S11 ) shows that the nanoparticle/COF composites are stable in nitrogen up to 400 ° C without obvious weight loss, as the pure TAPB-DMTP-COF does. The porosity of evacuated composites was investigated by nitrogen-sorption measurements. All composites display type IV isotherms ( Figure 4 a), as pure TAPB-DMTP-COF sample

IV isotherms ( Figure 4 a), as pure TAPB-DMTP-COF sample Figure 4. (a) Nitrogen-sorption isotherms for

Figure 4. (a) Nitrogen-sorption isotherms for the activated COF and COF composites individually containing 0.10 and 0.20 wt % 15 nm Au nanoparticles, 0.38 wt % 50 nm Au nanoparticles, and 0.26 wt % 25 × 100 nm Au nanorods at 77 K up to 1 bar. (b) Pore-size distributions for COF and COF composite containing 0.20 wt % 15 nm Au nanoparticles.

does, with steep increase in nitrogen uptake at low relative pressure (<0.01), indicating the existence of micropores, and a step in the relative pressure range of 0.10 0.20, corresponding to the condensation of nitrogen in mesopores. By applying the consistency criteria, 64 , 65 their Brunauer Emmett Teller (BET) surface areas were estimated. As shown in Table S1, compared with the pure COF sample, composites display slightly decreased BET surface areas due to the mass contributions of nonporous nanoparticles and PVP. The pore size distributions within composites were further evaluated from their isotherms using nonlocal density functional theory

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(NLDFT, based on N 2 -cylindrical pores-oxide surface model).

All samples exhibit the similar distribution patterns with a main pore width centered at 3.24 nm (Figure 4 b and Figure S13 ), suggesting that the incorporated nanoparticles functionalized with PVP do not occupy the channels of the 2D TAPB-DMTP- COF matrices due to their large sizes. The accessibility and catalytic activity of the encapsulated Au nanoparticles functionalized with PVP were probed in the well-

studied reduction reaction of 4-nitrophenol by

Although the aqueous solution of 4-nitrophenol undergoes a rapid color change (with a UV vis absorption peak shift from 319 to 400 nm) after adding NaBH 4 due to the formation of 4- nitrophenolate ions, the reduction reaction does not proceed substantially in the absence of suitable catalysts (such as Au, Ag, Pd, and Pt nanoparticles). Figure 5 a shows the UV vis spectra of the reaction solution in the presence of COF composite containing 0.20 wt % 15 nm Au nanoparticles. The absorption peak at 400 nm characteristic for 4-nitrophenolate was observed to decrease in intensity rapidly and disappear eventually after 10 min, suggesting that the COF composite does catalyze 4-nitrophenolate reduction. Since the COF itself, in the control experiment, exhibits no propensity to catalyze the reduction reaction, the above result indicates that the 4- nitrophenol molecules can di use quickly through the channels of TAPB-DMTP-COF matrix and react on surfaces of the active Au nanoparticles. In addition, the appearance of the new peak at 300 nm and the well-de ned isosbestic point at 315 nm in the UVvis spectra of the reaction solution suggests that the COF composite selectively catalyzes the reduction of 4- nitrophenol to give 4-aminophenol as the sole product. 66 Given that NaBH 4 concentration used in the reaction is much higher than that of 4-nitrophenol, pseudo- rst-order kinetics is expected for the above catalytic reaction. 43 , 59 , 61 Based on the linear relationship between ln[ A t / A 0 ] and time (where A t and A 0 are the absorbance of reaction solution at 400 nm at time t and 0, respectively) ( Figure S14 ), the apparent rate constant k was calculated to be 0.46 min 1 for the reaction catalyzed by COF composites containing 0.20 wt % 13 nm Au nanoparticles. The catalytic activity (in terms of TOF) of the obtained 0.20 wt % 13 nm Au/COF composite is higher than those of composites of Au nanoparticles encapsulated in mesoporous silica and porous carbon tested under similar conditions ( Table

NaBH 4 . 43 , 59 61

S2). 67 , 68

Taking advantage of the exibility of current encapsulation method, we further investigated the e ects of contents, sizes, and shapes of Au nanoparticles embedded in COF matrices on the catalytic performances of composites under the same conditions. As showed in Figure 5 b and Figure S14 , all composite samples can catalyze 4-nitrophenol reduction but display di erent activities. On the one hand, when composites contain the same type of Au nanoparticles, their catalytic performances are nanoparticle content dependent. For example, the composite containing 0.10 wt % 15 nm gold nanoparticles displays lower catalytic activity (with a smaller rate constant of 0.36 min 1 ) than the 0.20 wt % sample does (Figure S14a d). On the other hand, when dierent types of Au nanoparticles are incorporated individually in TAPB- DMTP-COF, the catalytic performances of the resulting composites are in uenced predominantly by the sizes and shapes of nanoparticles. For example, even with higher Au contents, composites containing 25 × 100 nm rods (0.26 wt %) and 50 nm nanoparticles (0.38 wt %) show a slightly decreased catalytic activity (with rate constant of 0.36 min 1 ) and much

E

(with rate constant of 0.36 min − 1 ) and much E Figure 5. Evaluation of

Figure 5. Evaluation of catalytic performances of Au nanoparticle/ COF composites in 4-nitrophenol reduction by NaBH 4 . (a) UVvis spectra of the reaction solution in the presence of composite containing 0.20 wt % 15 nm Au nanoparticles recorded at 2 min intervals. (b) Catalytic conversion of 4-nitrophenol versus reaction time with composites containing individually 0.20 wt % 15 nm Au nanoparticles, 0.26 wt % 25 × 100 nm Au nanorods, and 0.38 wt % 50 nm Au nanoparticles, as catalysts. (c) The reusability of composite containing 0.20 wt % 15 nm Au nanoparticles as catalyst for six consecutive cycles of reactions.

lower activity (with rate constant of 0.12 min 1 ) ( Figure S14e h ), respectively, in comparison with that incorporated with 15 nm nanoparticles (0.20 wt %). The 15 nm Au nanoparticles behave more active presumably as the result of their higher surface area volume ratio, in comparison with 25 × 100 nm rods and 50 nm nanoparticles. 59 , 61 The reusability of nanoparticle/COF composites as catalysts for the reduction of 4-nitrophenol was further conrmed by the observation of the similar conversion for the same reaction time (10 min) for six consecutive cycles (the slightly decreased conversions in the later catalysis cycles are presumably caused

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by the loss of catalyst (nanoparticle/COF) during the washing process between cycles) ( Figure 5c). The XRD and TEM measurements (Figure S16 ) show that the mesostructures and crystallinity of nanoparticle/COF composites were preserved after the catalytic reactions, and no obvious degradation was observed, suggesting their excellent stability.

CONCLUSION

In summary, catalytically active Au nanoparticles with di erent sizes and shapes have been encapsulated successfully in the 2D TAPB-DMTP-COF with tunable contents based on the surface functionalization of nanoparticles with PVP and the optimiza- tion of COF synthesis. The framework matrix of the resulting composites retains its thermal stability, high crystallinity, large surface area, and open mesoporous structures. The accessibility and catalytic activity of the embedded Au nanoparticles were examined in the reaction of 4-nitrophenol reduction by NaBH 4 . The COF composites display recyclable catalytic performance with activities relevant to the contents, sizes, and shapes of the encapsulated nanoparticles. With this simple model reaction, we validated the feasibility of the nanoparticle-encapsulation strategy for imparting catalytic functionality to 2D COF materials for the rst time. The Au nanoparticle/TAPB- DMTP-COF composites prepared here could be used for other catalytic reactions where the framework matrix is still chemically and thermally stable. In addition, the possible molecular sieving e ect originating from the framework matrices for the catalytic applications has not been evaluated further in this work due to the large pore sizes of TAPB- DMTP-COF (3.24 nm), which, however, could be anticipated for the composites prepared using current encapsulation method with other 2D or 3D COFs possessing smaller pore sizes (and with other nanoparticles). Finally, beyond the traditional catalysis, this simple and exible encapsulation method could be applied to prepare (multi)functional COF composites integrated with other nanoparticle-relevant (e.g., optical and magnetic) properties for various applications such as sensing, drug delivery, and bioimaging.

ASSOCIATED CONTENT

* S

Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b16267 . Synthetic procedures and characterization details, Figures S1S17, and Tables S1 and S2 ( PDF )

AUTHOR INFORMATION

Corresponding Authors

*E-mail zhugs100@nenu.edu.cn (G.Z.). *E-mail chilf@suda.edu.cn (L.C.). *E-mail glu@suda.edu.cn (G.L.).

ORCID

(L.C.). * E-mail glu@suda.edu.cn (G.L.). ORCID Kun Liu: 0000-0003-2940-9814 Guang Lu:

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS

This work is supported by the National Natural Science Foundation of China (Grant 21371127), the Collaborative Innovation Center of Suzhou Nano Science and Technology, a

project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and the Young Thousand Talented Program.

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