Ammonia
is a promising energy vector that can store the high energy
density of hydrogen. For this reason, numerous adsorbents have been
investigated as ammonia storage materials, but ammonia adsorbents
with a high gravimetric/volumetric ammonia capacity that can be simultaneously
regenerated in an energy-efficient manner remain underdeveloped, which
hampers their practical implementation. Herein, we report Ni_acryl_TMA
(TMA = thiomallic acid), an acidic group-functionalized metal–organic
framework prepared via successive postsynthetic modifications of mesoporous
Ni2Cl2BTDD (BTDD = bis(1H-1,2,3,-triazolo
[4,5-b],-[4′,5′-i])
dibenzo[1,4]dioxin). By virtue of the densely located acid groups,
Ni_acryl_TMA exhibited a top-tier gravimetric ammonia capacity of
23.5 mmol g–1 and the highest ammonia storage of
0.39 g cm–3 at 1 bar and 298 K. The structural integrity
and ammonia storage capacity of Ni_acryl_TMA were maintained after
ammonia adsorption–desorption tests over five cycles. Temperature-programmed
desorption analysis revealed that the moderate strength of the interaction
between the functional groups and ammonia significantly reduced the
desorption temperature compared to that of the pristine framework
with open metal sites. The structures of the postsynthetic modified
analogues were elucidated based on Pawley/Rietveld refinement of the
synchrotron powder X-ray diffraction patterns and van der Waals (vdW)-corrected
density functional theory (DFT) calculations. Furthermore, the ammonia
adsorption mechanism was investigated via in situ infrared and vdW-corrected
DFT calculations, revealing an atypical guest-induced binding mode
transformation of the integrated carboxylate. Dynamic breakthrough
tests showed that Ni_acryl_TMA can selectively capture traces of ammonia
under both dry and wet conditions (80% relative humidity). These results
demonstrate that Ni_acryl_TMA is a superior ammonia storage/capture
material.