Self-Assembled Open Porous Nanoparticle Superstructures

Self-Assembled Open Porous Nanoparticle Superstructures

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Fenghua Zhang, Rongjuan Liu, Yanze Wei, Jingjing Wei, and Zhijie Yang*

Cite This: J. Am. Chem. Soc. 2021, 143, 11662 −11669

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sı Supporting Information

ABSTRACT: Imparting porosity to inorganic nanoparticle assemblies

to build up self-assembled open porous nanoparticle superstructures

represents one of the most challenging issues and will reshape the

property and application scope of traditional inorganic nanoparticle

solids. Herein, we discovered how to engineer open pores into diverse

ordered nanoparticle superstructures via their inclusion-induced

assembly within 1D nanotubes, akin to the molecular host−guest

complexation. The open porous structure of self-assembled composites

is generated from nonclose-packing of nanoparticles in 1D conﬁned

space. Tuning the size ratios of the tube-to-nanoparticle enables the

structural modulation of these porous nanoparticle superstructures, with symmetries such as C , zigzag, C , C , and C . Moreover,

when the internal surface of the nanotubes is blocked by molecular additives, the nanoparticles would switch their assembly pathway

and self-assemble on the external surface of the nanotubes without the formation of porous nanoparticle assemblies. We also show

that the open porous nanoparticle superstructures can be ideal candidate for catalysis with accelerated reaction rates.

INTRODUCTION

that postassembly etching of binary NPs superlattices is able to

engineer nonclose-packed (NCP) NP arrays with porous

■

One of the challenging goals in materials chemistry and physics

is to form the desired superstructures from building blocks

structures. Another example shows that the self-assembly of

nonspherical (trigonal bipyramids) NPs is able to produce

with delicate design. In molecular systems involving building

blocks of organic molecules, this is explored through host−

guest chemistry for supramolecular materials and reticular

chemistry for porous frameworks (i.e., metal organic frame-

open porous clathrate-like structures. Furthermore, bridging

the colloidal NPs with porous materials provides an alternative

avenue to engineer the porous NPs composites. The

2−28

−6

organization of NPs in porous templates,

nanotubular structure from scrolling of nanosheets,

anodic aluminum oxide (AAO) with honeycomb-like struc-

such as

works, MOFs, and covalent organic frameworks, COFs).

2−24

Furthermore, macrocyclic molecules with open ended cavities,

including crown ethers, cyclodextrins, cyclophane, calixarenes,

cucurbit[n]urils, pillar[n]arenes, and metal−organic cages,

have been extensively explored as host materials to sequester

the complementary guests.

chemical property of a molecular host diﬀers from that of its

25,26

27,28

tures

and cyclodextrin-based supramolecular tubes,

have been engineered to produce several diﬀerent NPs

assemblies. These earlier reports mainly focused on engineer-

ing the structures of NPs assemblies, such as the one-

dimensional (1D) chain-like, cylindrical, and tube-like

structures, but is less concerned with the porous feature of

these NPs assemblies. Moreover, previous computational

simulations predicted that NP assemblies with tens of ordered

−10

In most cases, the external

internal cavity, facilitating the guest inclusion via hydrophobic

1,12

force.

Additionally, guest recognition and constrictive

binding with the supramolecular host can fundamentally

revolutionize the chemical and physical properties of trapped

guest molecules, including acceleration of chemical reactions,

modulation of selectivity in catalysis (size-, site-, regio-, and

enantioselectivity), and regulation of light-matter interac-

structures could be produced as the ratio of the cylinder

29,30

diameter to the sphere diameter is varied.

interestingly, because of the conﬁnement eﬀect, structures

with C and C symmetries have NCP open porous features,

3−15

tions.

The translation of such ideas to nanosized building

which has not been reported previously. Hence, systematic

engineering on NPs assemblies in 1D nanotubular conﬁnement

blocks and colloidal nanoparticles (NPs) would potentially

open the gateway to new materials and/or new properties.

However, it is still an ongoing challenge and the pathways to

achieve this goal are largely unexplored.

Received: May 8, 2021

Published: July 26, 2021

Spontaneous assembly of inorganic NPs has been applied to

construct ordered superstructures with tens of diﬀerent

crystalline structures, but the packing of these NPs frequently

adopts dense, close-packed arrangements without any open

17−19

pores at thermodynamic equilibrium.

One example shows

2021 American Chemical Society

J. Am. Chem. Soc. 2021, 143, 11662−11669

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is highly desired, which potentially provides a productive

avenue for NPs based porous solids.

Here, we show that self-assembled NP superstructures with

an open porous feature can be formed by conﬁned assembly of

NPs within nanotubes (NTs), akin to the molecular host−

guest assembly. Tuning the size ratios of NTs-to-NPs allows

for the structural engineering of these open porous NP

superstructures, with symmetries such as C , zigzag, C , C , and

C₅. Additionally, assembly of NPs either at the internal surface

or external surface of NTs can be deliberately controlled

through the introduction of competitive molecular additives,

leading to the competitive assembly.

Last but not least, these 1D porous NPs superstructures

show enhanced catalytic activity for silane alcoholysis and

semihydrogenation reactions.

RESULTS AND DISCUSSION

■

Assembly of NPs into Porous NPs Superstructures.

Co(OH) NTs tethered with a layer of octylamine were

synthesized according to a previous published method with

modiﬁcations. Transmission electron microscopy (TEM)

reveals that the particles are tubular structures with external

diameter and wall thickness of ∼18.6 nm and ∼1.0 nm,

respectively (Figure 1a−c). The length of these NTs is in the

range of hundreds of nanometers (Figure 1d). These NTs are

able to disperse in a nonpolar organic solvent, i.e., hexane.

The octylamine grafting density, determined from thermog-

ravimetric analysis (TGA), is measured to be ∼2.4 octylamine

Figure 1. Design concept for NCP 1D assembly of NPs within

per nm , assuming that the grafting density of octylamine

Co(OH) NTs. (a) The schematic diagram of Co(OH) NTs with

molecules on NTs is identical throughout the surface

distinct curvatures at their internal and external surfaces. (b, c) TEM

(

Supporting Information, SI Note S1). Importantly, the

images of Co(OH) NTs. (d) Size histogram of diameter and length

geometric curvature of the external and internal surface of

the NTs diﬀers, which consequently modiﬁes the respective

molecular orientations. For the external surface with positive

curvature, the molecular packing diverges, and the distance

between the two neighboring molecules increases remarkably

in the tail region (Figure 1e and SI Note S1). In sharp contrast,

for the internal surface with negative curvature, the molecular

packing converges and the distance between two neighboring

molecules decreases in the tail region (Figure 1e). It is this

connection between local curvature and molecular orientations

of NTs that provides the basis for the current construct. A

spherical NP would prefer to attach to the internal surface of

the NTs rather than the external surface with optimized van

der Waals interactions from alkyl chain intergiditation (SI

Note S2). Therefore, these NPs would spontaneously assemble

within the NTs, giving rise to NP superstructures within the

NTs, resembling the molecular host−guest assembly (left,

Figure 1f). However, when the intermolecular space at the

internal surface of NTs is blocked by molecular additives, the

aﬃnity between NPs and NTs is largely diminished, which

consequently drives the assembly of NPs at the external surface

of NTs (middle, Figure 1f) or self-sorted assembly (right,

Figure 1f), termed as competitive self-assembly and phase

separation, respectively.

of Co(OH) NTs. (e) Ligand packing density at the external and

internal surface of Co(OH) NTs. (f) Schematic representations of

possible modes of assembly of NPs and NTs. NPs can interact with

either internal or external surface of NTs, leading to respective host−

guest or competitive self-assembly; aggregation of NTs would lead to

phase separation.

^C^o⁽^O^H⁾2 NTs was carried out through a bad solvent

permeation method. Au5 NPs and NTs with a mass ratio of

:1 produce the best assembly structure (Figure S7). Typically,

Au5 NPs and NTs with a mass ratio of 1:1 were dispersed in

hexane, followed by a process of ethanol vapor diﬀusion at 50

C (Figure S8a −f). Time resolved UV−vis spectroscopy

studies reveal that Au5 NPs were gradually precipitating out

−

−1

of hexane with a rate of ∼6.0 × 10 mol h (Figure S8g).

After 8 h, nearly all the Au5 NPs were encapsulated into NTs,

resulting in Au5/NTs composites, as can be observed in TEM

images (Figures 2a,b and S8f). Several diﬀerent orientations

reveal that these Au5 NPs are self-assembled into 1D

superstructures with C symmetry, and the unit cell consists

of four NPs, where two NPs occupy the circular cross section

of the NTs and the other two NPs are packed orthogonally

(

Figure 2c). Importantly, this C symmetric packing of Au5

The host−guest assembly was ﬁrst engineered with Au NPs

NPs within NTs gives rise to the porous structures, as

evidenced by the nitrogen sorption isotherm with a mode of

type IV (Figure 2d). The pore size distribution based on the

Non Localized Density Functional Theory (NLDFT) method

clearly reveals the sizes of mesopores centered at 4.0 nm

(Figure 2e), which is much smaller than that of bare NTs

without the encapsulation of Au5 NPs.

coated with dodecanethiol of 5.1 ± 0.4 nm in diameter,

termed as Au5 NPs (Figure S6a,b), resulting in an eﬀective

diameter ratio (γ) between NTs and NPs, γ =

≈ 2.0 (the

d_N_P

eﬀective diameter of a NP (d ) is determined by the sum of

the metal core diameter and twice the thickness of the organic

ligand (Figure S6c). The assembly of Au5 NPs within

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Figure 2. NPs-NTs host−guest self-assembly. (a, b) TEM images of assembly of Au5 NPs inside the Co(OH) NTs.(c) C symmetric packing

mode of Au5 NPs within NTs. The upper part is two diﬀerent views of C symmetric structures. The bottom part is the TEM images of three

diﬀerent orientations of Au5/NTs and the corresponding model. (d) nitrogen adsorption−desorption isotherms of NTs and Au5/NTs composites.

−1

(

e) Pore size distributions of NTs and Au5/NTs. The BET surface areas of Au5/NTs and NTs are calculated to be 144.0 and 54.0 m g ,

respectively. (f) TEM images of Au NPs assemblies with diverse structures at diﬀerent γ = 1.1, 1.5, 1.8, 2.3, and 2.7. The bottom part is the

corresponding structural models. (g−j) TEM images of assemblies of Fe O NPs (g), Fe O nanocubes (h), 2D Gd O nanoplatelets (i), and 1D

CdSe nanorods (j). The scale bars are 20 nm.

Next, we systematically tuned the sizes of Au NPs to further

engineer the open porous NP superstructures from host−guest

assembly within the NTs. To this end, Au NPs diﬀering by

their sizes, such as 3.1 (Au3), 4.5 (Au4), 6.0 (Au6), 7.1 (Au7),

and 13.5 nm (Au13) (Figures S9 −S16 ), were synthesized,

resulting in respective eﬀective diameter ratios of ∼2.7, ∼2.3,

and ﬁve NPs occupying the circular cross section of the NTs,

respectively, leaving a central hollow channel (Figure 2f).

These results are in agreement with a previous report on

29,30

computer modeling of packing spheres in a cylinder.

Because the size ratio between NTs and NPs is smaller than

the bottom limits (γ = 2.873) that gives rise to the hexagonal

close-packed (HCP) structures, which consequently generates

NCP 1D NPs superstructures with diverse symmetries,

accompanied by the presence of mesoporous structures

∼

1.8, ∼1.5, and ∼1.1. A smallest γ ≈ 1.1 results in the 1D NPs

chains with typical lengths of up to ∼200 nm (Figure 2f).

On increasing the eﬀective diameter ratio γ to 1.5, zigzag

ordering of the NP chains can be seen, where each NP has two

contacted neighboring NPs. Strikingly, when γ is equal to 1.8,

double helical structures, resembling the packing of DNA

double helices. A further increase of γ to 2.3 and 2.7 results in

the NPs superstructures with C₄and C₅symmetry,

respectively. The C and C symmetry packing is due to four

(

details see SI Note S3). We note that all these nano-

composites with diverse symmetries or structures, Au3/NTs,

Au4/NTs, Au5/NTs, Au6/NTs, Au7/NTs, and Au13/NTs,

show similar open porous features with a mean pore size of ∼4

nm (Figure S17 and Table S4).

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Figure 3. NPs-NTs competitive self-assembly. (a) Schematic of assembly of NPs at the external surface of NTs by introducing molecules to block

the internal surface of NTs. (b) H NMR spectra of limonene (black line) and limonene assembly on the NTs (red line)in CDCl ; (c) CD spectra

of (S)-limonene and trapping of (S)-limonene within the NTsin CHCl ; (d−f) TEM image (d, f) and HADDF image (e) of Au3@NTs; (g−i)

TEM image (g, h), (i) HADDF and HAADF-EDS chemical mapping of cobalt and iron of Fe O @NTs. The scale bars are 20 nm.

Additionally, we demonstrate that the scope of “guest” NPs

can be extended to other NPs including the nonspherical ones.

To this end, a series of spherical NPs, including 13.5 nm Fe O

S20). Overall, we show that more than 90% of NPs with

nonspherical shapes can be encapsulated in the host NTs. For

Fe O nanocubes, the face-to-face packing is dominant,

coated with oleic acid (Figure 2g), 3.2 nm Pd coated with

oleylamine/oleic acid, 3.4 nm Pt coated with oleylamine

resulting in the formation of single chain nanocube assemblies

within the NTs (Figure 2h). For 2D nanoplates, we found that

the face-to-face packing is more favored, resulting in 1D

stacked structures (Figure 2i). While for 1D CdSe nanorods

stacked into 1D spiral structures (Figure 2j).

Figures S18 −S20), and nonspherical NPs, including Fe O

nanocubes with a mean edge length of 12.8 nm, 1D CdSe

nanorods with diameter and length of 2.1 and 11.0 nm,

respectively, and two-dimensional (2D) Gd O₃triangular

nanoplatelets with an edge length of 13.0 nm were synthesized

and applied as “guests” for the assembly (Figures S19 and

Competitive Assembly of NPs. The encapsulation of

NPs into NTs is mainly on the basis of optimal van der Waals

interactions given by the fact that most of the alkyl chains

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Figure 4. Catalytic properties of open porous NPs superstructure. (a) Time-dependent DPS alcoholysis over Au3/NTs and Au3@NTs catalyst. (b)

Catalytic eﬃciencies of Au3/NTs and Au3@NTs catalyst in various polar alcohol solvent. (c) Alcoholysis TOF for Au/NTs with diﬀerent sizes of

Au NPs. (d) Snapshots from atomistic simulations of trapping DPS molecules within the self-assembled alkyl chains, akin to a C symmetric NPs

superlattices with a central open channel. (e) Statistical analysis of numbers of trapped DPS molecules within alkyl chains at various time intervals.

tethered onto the surfaces are parallel and are intercalated

Additionally, we make several observations: (1) the amount

of limonene molecules is found to be crucial to the assembly

(Figures S22 and S23); (2) similar competitive self-assembly

was also achieved when (S)-limonene was replaced by (R)-

limonene or other molecular additives with comparable sizes,

(

∼−2.8 k T per methylene group, k is the Boltzmann

constant). We postulate that the convergent alkyl chains at the

internal surface of NTs could be considered as “supramolecular

ﬂasks” with a window size of ∼0.33 nm (SI Note S4). Hence,

when these internal supramolecular ﬂasks are engaged with

other molecular additives with proper sizes, their interactions

with NPs will be interrupted, which leads to competitive self-

assembly rather than host−guest assembly (Figure 3a). To test

this idea, homochiral organic molecules, (S)-limonene, with a

i.e., β -pinene with a molecular size of 0.94 × 0.69 × 0.61 nm

(Figure S24a,b); (3) smaller sized additives, such as toluene

(0.82 × 0.67 × 0.39 nm ), cyclohexene (0.72 × 0.67 × 0.52

nm ), and chlorocyclohexane (0.83 × 0.69 × 0.55 nm ), would

result in phase separations rather than host −guest assembly or

competitive self-assembly (Figure S24c −h ). The phase

separation is mainly driven by the primary packing of NTs

through their alignment with the long axis (Figure 1f).

Considering that the length of the ligands (octylamine) coated

on NTs is ∼1 nm, when the length of the molecular additives

is similar to that of the octylamine, the encapsulation of the

molecular additives into the external surface of NTs would

hamper the van der Waals interactions between NTs, and

consequently lead to the deposition of NPs onto the NTs as a

monolayer structure. On the contrary, smaller sized molecular

additives with lengths smaller than 1 nm would not eﬀectively

reduce the van der Waals attraction between NTs, leading to

phase separation.

size of 1.04 × 0.67 × 0.54 nm , were added into NTs hexane

dispersion with a concentration of 40 mM, followed by the

ethanol vapor diﬀusion. The NTs were separated by

centrifugation and were rinsed in ethanol for at least 2 h.

Proton nuclear magnetic resonance measurement conﬁrms the

presence of (S)-limonene within the NTs (Figure 3b).

Remarkably, these (S)-limonene molecules trapped in NTs

were aggregated, as evidenced by the apparent redshift (∼80

nm) in circular dichroism (CD) spectroscopy (Figure 3c).

When these NTs/(S)-limonene composites were applied as

host to direct assembly of NPs, distinct results emerge for both

.1 nm Au NPs and 8.0 nm Fe O NPs (Figure 3d−i). Almost

all the NPs were rejected by the internal cavities and were

located at the external surface of NTs, termed as Au3@NTs

and Fe O @NTs. Close inspection reveals that these NPs were

Catalytic Properties of Open Porous NPs Super-

structures. Because of the structural diversity coupled with

open porous features of the NPs/NTs composites, they are

expected to ﬁnd use in a wide range of applications, such as

organic catalysis, akin to the supramolecular catalysis within

self-assembled into HCP monolayer superlattices (Figure 3f).

The nitrogen sorption isotherm of Au3@NTs suggests a mode

of type IV, while their mean pore size (∼14.2 nm) is

nontrivially greater than that of Au3/NTs nanocomposites

33−36

the cavitands.

As reported previously, alkyl chains usually

(∼3.9 nm) (Table S4 and Figure S21).

play the role of catalytic regulator in Au catalyzed silane

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−1

alcoholysis reactions. However, these siliane alcoholysis

reactions are performed in polar solvents, which usually

cause the aggregation of Au NPs coated with alkyl chains and

consequently deactivates the catalyst. Here, we found that

open porous Au NP superstructures assembled within NTs

showed good catalytic activity and cyclic stability in silane

= 0.5 nm ) functionalized with a layer of dodecanethiol in a

10 × 10 × 15 nm box of methanol with 10 DPS molecules

(Figure 4d, Movie S1). At the beginning, these DPS molecules

are randomly distributed in the methanol medium. After 20 ns,

we found that a large portion of DPS molecules (∼70%) are

adsorbed onto the alkyl chain layers (Figure 4e). Additionally,

we found that these DPS molecules are more likely to be

adsorbed at interdigitated chains. This suggests a possible role

of alkyl chains pinned on surfaces in harvesting less polar

molecules, i.e., DPS, in polar medium (methanol), which

consequently leads to the enrichment of the less polar

molecules at the near loci of the alkyl chains. Therefore, the

open porosity coupled with enhanced molecular trapping

renders these self-assembled NP superstructures highly

eﬃcient in catalysis.

alcoholysis. First, Au3 NP superstructures with C symmetry

Au3/NTs) were applied for the methanolysis of diphenylsi-

(

lane (DPS). A series of control experiments were also

conducted, including NTs, Au3 NP assemblies (from the

same conditions as described for Au3/NTs but in the absence

of NTs, Figures S25 and S26), and Au3@NTs. The results

clearly suggested that the catalytic eﬃciencies of Au3/NTs

were much higher than that of Au3@NTs, Au3 assemblies, or

NTs (Figure 4a and Table 1). Importantly, the speciﬁc

This catalytic enhancement was further demonstrated by

semihydrogenation reactions over self-assembled open porous

Pd NPs superstructures (Pd3/NTs, characterization, Figures

S18 and S29 −S30 ). Although it is well-known that Pd NPs or

Pd-based materials are demonstrated to be ideal catalysts for

alkyne semihydrogenation reactions, they still suﬀer from the

low TOF as well as the low Z-selectivity and over-

Table 1. Alcoholysis of Silanes Catalyzed by Au/NTs

Catalysts

38,39

_R1

_R2

_R3

_T_O_F₍_h−1

)

reduction.

We show that Pd3/NTs possess good catalytic

entry

catalyst

time (min)

−

activity (77 300 h ) and stereoselectivity (Z/7E > 99) at low

temperature. By contrast, these Pd NPs superstructures with

open porous structures (Pd3/NTs) show much higher

catalytic TOF than that of Pd3@NTs, where Pd NPs are

self-assembled into a hexagonal-close-packed structure at the

external surface of the NTs (Table 2). Furthermore, the

catalyst could be recycled for over 7 cycles without apparent

decrease in activity (Figure S31).

Au3 SCs

NTs

Au3@NTs

Au3/NTs

Au4/NTs

Au5/NTs

Au6/NTs

Au7/NTs

Au13/NTs

56 500

111 600

105 700

95 600

100 500

87400

n-propyl

n-butyl

91 300

Table 2. Pd NPs-Catalyzed Selective Hydrogenation of

105 700

133 700

126 200

121 500

114 100

132 700

Alkynes to Alkenes

b: R = C H , R =

a: R = CO CH , R = CO CH

C H

Reaction conditions: silanes (10 mmol) in alcohol (5.0 mL) with 0.2

1c: R = Ph, R = (CH

) CH

1d: R = Ph, R = H

mg of catalysts at 30 °C. 50% of the silane was converted.

TOF (h⁻¹

)

entry

catalyst

NTs

time (min)

Z/E

−

turnover frequency (TOF) for Au3/NTs reaches 111 600 h ,

calculated on the basis of surface Au atoms, which is roughly

twice the activity of the reported highest value (55 000 h ).

Pd3/NTs

Pd3@NTs

Pd3/NTs

Pd3@NTs

Pd3/NTs

Pd3@NTs

>99/1

77 300

41 000

67 000

42 000

63 000

36 000

72 000

44 700

−

Equally important, the Au3/NTs could be recycled for over 7

cycles using centrifugation, and there was no signiﬁcant

decrease in activity (Figure S27). Furthermore, a variety of

substrates, diﬀerent silanes, and alcohols were tested, and the

results in Table 1 and Figure 4b show the high catalytic

activities for the open porous Au3/NTs composites. When

other open porous Au NP superstructures with diverse

symmetries were applied for the same alcoholysis reaction,

we found that the TOF of these catalysts were very similar,

Reaction conditions: alkenes (5 mmol), Ph SiH (10 mmol), and

DIPEA (N,N-diisopropylethylamine) (10 mmol) in the presence of

the 0.1 mg of catalysts in acetone (10.0 mL) at 30 °C. 50% of the

alkyne was converted.

−

ranging from ∼110 000 to ∼135 000 h (Figure 4c), despite

the fact that smaller sized Au NPs lead to faster reaction

kinetics associated with larger speciﬁc areas of Au (Figure

S28 ).

CONCLUSIONS

■

To better understand the high TOF of these open porous

NP superstructures, we studied the aﬃnity of DPS molecules

In summary, we have explored how to engineer open porosity

in NP solids through encapsulation of NPs into 1D NTs with

open ended channels. The geometry of the NP assembly in the

conﬁned 1D channel is mainly determined by the size ratio γ

between NTs and NPs, which consequently leads to self-

to C symmetric open porous NP superstructures by atomistic

molecular dynamics (MD) simulations. To this end, we built a

C₄symmetric structure of four curved Au surfaces (curvature κ

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Dalgliesh, R.; Mahmoudi, N.; Pesce, L.; Perego, C.; Pavan, G. M.;

Article

assembled NP superstructures. Importantly, we have shown

that these NPs/NTs with an open porous feature can

remarkably promote organic catalysis with state of the art

high TOF, akin to the supramolecular catalysis within

molecular cavitands. We envisage that a productive avenue

for future research is the use of open porous NP super-

structures to encapsulate biomacromolecules, i.e., proteins,

which may meet the daunting challenge for their incommen-

surably larger size compared with common synthetic supra-

molecular hosts. Once encapsulated within open porous NP

superstructures, their interactions with ordered NP super-

structures may potentially alter their structures and functions.

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AUTHOR INFORMATION

Corresponding Author

Zhijie Yang − Key Laboratory of Colloid and Interface

Chemistry, Ministry of Education, School of Chemistry and

Chemical Engineering, Shandong University, Jinan 250100,

P. R. China; orcid.org/0000-0002-5012-9852;

Email: zyangchem@sdu.edu.cn

■

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Fenghua Zhang − Key Laboratory of Colloid and Interface

Chemistry, Ministry of Education, School of Chemistry and

Chemical Engineering, Shandong University, Jinan 250100,

P. R. China

Rongjuan Liu − Key Laboratory of Colloid and Interface

Chemistry, Ministry of Education, School of Chemistry and

Chemical Engineering, Shandong University, Jinan 250100,

P. R. China

Yanze Wei − Key Laboratory of Colloid and Interface

Chemistry, Ministry of Education, School of Chemistry and

Chemical Engineering, Shandong University, Jinan 250100,

P. R. China

Jingjing Wei − Key Laboratory of Colloid and Interface

Chemistry, Ministry of Education, School of Chemistry and

Chemical Engineering, Shandong University, Jinan 250100,

P. R. China; orcid.org/0000-0002-2197-8062

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ACKNOWLEDGMENTS

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This work was ﬁnancially supported by the National Natural

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