Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 125, Issue 32, Pages 17939-17949Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c03118
Keywords
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Funding
- EMR grant of CSIR-India of the Science and Engineering Research Board (SERB), India [01(2984)/19/EMR-II]
- Core Research Grant of SERB of the Science and Engineering Research Board (SERB), India [CRG/2020/002943]
- IITG
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This study demonstrates the potential of using layered double hydroxides for ion pumping, achieving efficient anionic transport and energy harvesting. The results show that it can achieve high power density under conditions of salinity gradient.
Numerous research efforts have been devoted to replicate the functioning of biological ion pumps in nanofluidic devices. Unlike previous reports of cationic pumps, positively charged CoAl layered double hydroxide (CoAl LDH) is exploited here for uphill pumping of anionic species. Nanofluidic membranes prepared by self-assembling exfoliated layers of CoAl LDH exhibit excellent anionic transport characteristics. At the surface-charge-governed regime, the positively charged CoAl LDH membrane (p-LDHM) showed a remarkable OH- ion conductivity of similar to 2 mS cm(-1). The remarkable mobility of OH- ions (4 x 10(-4) cm(2) V-1 S-1) in the atomically thin channel of p-LDHM is attributed to the tiny activation energy (0.09 eV) required for Grotthuss-like hopping of the ions between the positive charges of densely packed CoAl LDH layers. The lamellar p-LDHM was also found to be suitable for energy harvesting via salinity gradient, and a power density up to 0.7 Wm(-2) was achieved under a 1000-fold concentration gradient. The triangular p-LDHM displays a diode-like nonlinear I-V curve, attributed to a combination of unipolar conductivity of counterions inside the two-dimensional (2D) nanochannels and geometrical asymmetry. The triangular p-LDHM pumps anions against the concentration gradient (up to 1000-fold), under fluctuating external potentials with a mean value of zero.
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