Intrinsically Microporous Polymer Retains Porosity in Vacuum Thermolysis to Electroactive Heterocarbon.
Vacuum carbonization of organic precursors usually causes considerable structural damage and collapse of morphological features. However, for a polymer with intrinsic microporosity (PIM-EA-TB with a Brunauer-Emmet-Teller (BET) surface area of 1027 m(2)g(-1)), it is shown here that the rigidity of the molecular backbone is retained even during 500 °C vacuum carbonization, yielding a novel type of microporous heterocarbon (either as powder or as thin film membrane) with properties between those of a conducting polymer and those of a carbon. After carbonization, the scanning electron microscopy (SEM) morphology and the small-angle X-ray scattering (SAXS) Guinier radius remain largely unchanged as does the cumulative pore volume. However, the BET surface area is decreased to 242 m(2)g(-1), but microporosity is considerably increased. The new material is shown to exhibit noticeable electrochemical features including two pH-dependent capacitance domains switching from ca. 33 Fg(-1) (when oxidized) to ca. 147 Fg(-1) (when reduced), a low electron transfer reactivity toward oxygen and hydrogen peroxide, and a four-point-probe resistivity (dry) of approximately 40 MΩ/square for a 1-2 μm thick film.
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
Yuanyang
Y
Rong
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
Daping
D
He
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
Adrian
A
Sanchez-Fernandez
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
Craig
C
Evans
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
Karen J
KJ
Edler
School of Chemistry, University of Edinburgh , West Mains Road, Edinburgh, EH9 3JJ, United Kingdom.
Richard
R
Malpass-Evans
School of Chemistry, University of Edinburgh , West Mains Road, Edinburgh, EH9 3JJ, United Kingdom.
Mariolino
M
Carta
School of Chemistry, University of Edinburgh , West Mains Road, Edinburgh, EH9 3JJ, United Kingdom.
Neil B
NB
McKeown
School of Chemistry, Cardiff University , Main Building, Park Place, Cardiff CF10 3AT, United Kingdom.
Tomos J
TJ
Clarke
School of Chemistry, Cardiff University , Main Building, Park Place, Cardiff CF10 3AT, United Kingdom.
Stuart H
SH
Taylor
National Physical Laboratory , Teddington, TW11 0LW, United Kingdom.
Andrew J
AJ
Wain
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
John M
JM
Mitchels
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, United Kingdom.
Frank
F
Marken