A Microporous Amic Acid Polymer for Enhanced Ammonia Capture

TY - JOUR

T1 - A Microporous Amic Acid Polymer for Enhanced Ammonia Capture

AU - Lee, Jiwoong

AU - Gokhan, Barin

AU - W. Peterson, Gregory

AU - Xu, Jun

AU - A. Colwell, Kristen

AU - Long, Jeffrey R.

PY - 2017/10/4

Y1 - 2017/10/4

N2 - Amic acids, consisting of carboxylic acids and amides, are often utilized as intermediates that can further undergo a dehydration-cyclization step to yield polymeric cyclic imides. Compared with imide-based materials, the presence of Brønsted acidic groups and multiple hydrogen-bond donors and acceptors in materials incorporating amic acids opens up the possibility for a variety of host-guest interactions. Here we report a facile and catalyst-free synthesis of a Brønsted acidic porous poly(amic acid) (PAA) and present its NH3 uptake properties using gas adsorption and breakthrough measurements. Simple addition of water as a cosolvent to a mixture of tetrakis(4-aminophenyl)methane and pyromellitic anhydride resulted in the formation of PAA in almost quantitative yield. Further mechanistic studies with model compounds revealed the importance of additive water to generate amic acid species selectively without forming cyclic imides at high temperatures. Gas adsorption isotherms and breakthrough curves obtained under dry and humid conditions demonstrate the enhanced NH3 uptake in the case of PAA compared with the related polycyclic imide at both low and high pressures. Furthermore, the results of adsorption/desorption cycling experiments provide insights into the strength of the interaction between ammonia and the polymers.

AB - Amic acids, consisting of carboxylic acids and amides, are often utilized as intermediates that can further undergo a dehydration-cyclization step to yield polymeric cyclic imides. Compared with imide-based materials, the presence of Brønsted acidic groups and multiple hydrogen-bond donors and acceptors in materials incorporating amic acids opens up the possibility for a variety of host-guest interactions. Here we report a facile and catalyst-free synthesis of a Brønsted acidic porous poly(amic acid) (PAA) and present its NH3 uptake properties using gas adsorption and breakthrough measurements. Simple addition of water as a cosolvent to a mixture of tetrakis(4-aminophenyl)methane and pyromellitic anhydride resulted in the formation of PAA in almost quantitative yield. Further mechanistic studies with model compounds revealed the importance of additive water to generate amic acid species selectively without forming cyclic imides at high temperatures. Gas adsorption isotherms and breakthrough curves obtained under dry and humid conditions demonstrate the enhanced NH3 uptake in the case of PAA compared with the related polycyclic imide at both low and high pressures. Furthermore, the results of adsorption/desorption cycling experiments provide insights into the strength of the interaction between ammonia and the polymers.

U2 - 10.1021/acsami.7b02603

DO - 10.1021/acsami.7b02603

M3 - Journal article

C2 - 28388032

SN - 1944-8244

VL - 9

SP - 33504

EP - 33510

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 39

ER -