As an important class of novel porous materials

nanonetwork-structured polymer and carbon materials have an unique three-dimensional (3D) interconnected hierarchical porous structure

and thus hold considerable promise in a spectrum of applications including energy

adsorption

separation

catalysis

medicine

and so on. This study focuses on the innovative structure design

controllable fabrication and structure-property relationship of novel nanonetwork-structured polystyrene and carbon materials. Hollow nanonetwork-structured polystyrene (HNNS-PS)

with hollow microporous PS spherical network unit was designed and fabricated on molecular-level by combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and Friedel-Crafts hypercrosslinking reaction. The 3D nanonetwork structure was controlled by precisely tuning the molecular weight of PS. Gel permeation chromatography (GPC)

scanning electron microscopy (SEM)

transmission electron microscopy (TEM)

thermogravimetric analysis (TGA)

and nitrogen adsorption were used to characterize the structure and morphology of HNNS-PS

and intelligent gravimetric analyzer (IGA) was used to determine the adsorption capacity of HNNS-PS towards toluene vapor. Additionally

the inheritance of 3D nanonetwork structure during carbonization was realized by tuning the heating rate. It is found that

by utilizing the SI-ATRP technique

one was able to precisely tune the PS molecular weight and to fabricate SiO

2

-

g

-PS building blocks with different PS molecular weight

i.e.

SiO

2

-

g

-PS-22.4k

SiO

2

-

g

-PS-46.9k and SiO

2

-

g

-PS-94.4k. As the molecular weight of PS went up from 2.26 × 10

4

to 4.69 × 10

4

and 9.44 × 10

4

the diameter of the nanospheres increased from 196 nm to 223 and 282 nm. After the Friedel-Crafts hypercrosslinking reaction and silica etching

HNNS-PS with different PS molecular weight was obtained. Due to the introduction of the micropores

the diameter of the network units increased to 263

280 and 332 nm

respectively. As the molecular weight of PS went up

the Brunauer-Emmett-Teller surface area (

S

BET

) of HNNS-PS increased from 346 m

2

g

−1

to 390 and 450 m

2

g

−1

. HNNS-PS had a high adsorption capacity of up to 534 mg g

−1

towards toluene vapor at 25 °C. In addition

when the heating rate was low (1 or 2 K min

−1

) during carbonization

the as-prepared carbon materials could preserve their 3D nanonetwork structure morphologies with

S

BET

up to 696 m

2

g

−1

which paved the way for the design and fabrication of 3D nanonetwork structured carbon materials

and thus would have important theoretic significance and application value.