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Shifted equilibria of organic acids and bases in the aqueous surface region.

ABSTRACT: Acid-base equilibria of carboxylic acids and alkyl amines in the aqueous surface region were studied using surface-sensitive X-ray photoelectron spectroscopy and molecular dynamics simulations. Solutions of these organic compounds were examined as a function of pH, concentration and chain length to investigate the distribution of acid and base form in the surface region as compared to the aqueous bulk. Results from these experiments show that the neutral forms of the studied acid-base pairs are strongly enriched in the aqueous surface region. Moreover, we show that for species with at least four carbon atoms in their alkyl-chain, their charged forms are also found to be abundant in the surface region. Using a combination of XPS and MD results, a model is proposed that effectively describes the surface composition. Resulting absolute surface concentration estimations show clearly that the total organic mole fractions in the surface region change drastically as a function of solution pH. The origin of the observed surface phenomena, hydronium/hydroxide concentrations in the aqueous surface region and why standard chemical equations, used to describe equilibria in dilute bulk solution are not valid in the aqueous surface region, are discussed in detail. The reported results are of considerable importance especially for the detailed understanding of properties of small aqueous droplets that can be found in the atmosphere.

SUBMITTER: Werner J

PROVIDER: S-EPMC6146375 | biostudies-other | 2018 Sep

REPOSITORIES: biostudies-other

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Shifted equilibria of organic acids and bases in the aqueous surface region.

Werner Josephina J Persson Ingmar I Björneholm Olle O Kawecki Delphine D Saak Clara-Magdalena CM Walz Marie-Madeleine MM Ekholm Victor V Unger Isaak I Valtl Corina C Caleman Carl C Öhrwall Gunnar G Prisle Nønne L NL

Physical chemistry chemical physics : PCCP 20180901 36

Acid-base equilibria of carboxylic acids and alkyl amines in the aqueous surface region were studied using surface-sensitive X-ray photoelectron spectroscopy and molecular dynamics simulations. Solutions of these organic compounds were examined as a function of pH, concentration and chain length to investigate the distribution of acid and base form in the surface region as compared to the aqueous bulk. Results from these experiments show that the neutral forms of the studied acid-base pairs are ...[more]

PMID: 30191936

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Project description:Organic Lewis bases [2,2'-bipyridine (BPY), 4-hydroxy-1,5-naphthyridine-3-carbonitrile (DQCN), and thenoyltrifluoroacetone (TTFA)] with bi-coordination sites of N and O were employed as perovskite surface defect passivants to address the efficiency and stability issues of perovskite solar cells (PSCs), with typical phenethylammonium iodide (PEAI) and piperazinium iodide (PI) passivants as reference. The surface properties of the perovskite films before and after passivation were characterized by Fourier-transform infrared, ultraviolet-visible, photoluminescence (PL), and time-resolved PL spectroscopy, X-ray diffraction, ultraviolet photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy. The characterizations reveal that BPY, DQCN, or TTFA forms coordination bonds with exposed "Pb2+", leading to a slight decrease in the highest occupied molecular orbital or lowest unoccupied molecular orbital energy level and bandgap. These passivants (especially TTFA) can passivate the perovskite surface defects to inhibit non-radiative recombination while having almost no influence on the grain size and surface morphology. Utilizing the passivated perovskite as the light absorption layer, solar cells with an inverted configuration of indium tin oxide/NiO x /passivated MAPbCl x I3-x /C60/BCP/Ag have been fabricated, and power conversion efficiencies of 19.22, 17.85, 16.49, 16.31, and 17.88% have been achieved from PEAI, PI, BPY, DQCN, and TTFA, respectively. All the device performance based on passivated perovskite is superior to that of the control (15.75%) owing to the reduced carrier recombination. The device from TTFA exhibits almost comparable efficiency to that of PEAI and PI controls, indicating that TTFA has an equal excellent passivation effect to state-of-the-art PEAI and PI. Furthermore, the devices based on BPY, DQCN, and TTFA show superior long-term stability with an efficiency loss of only 13.2, 16.7, and 12.9%, respectively, after being stored for 40 days in a ∼12% humidity, low-oxygen level environment, which is 45.4, 38.8, and 44.4% for the control, PEAI, and PI devices, respectively, primarily due to the improved hydrophobicity of the perovskite surface. Our results demonstrate that it is feasible to achieve high-efficiency and long-term-stable perovskite solar cells via selecting the appropriate molecules to passivate perovskite surface defects.

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Shifted equilibria of organic acids and bases in the aqueous surface region.

Publications

Shifted equilibria of organic acids and bases in the aqueous surface region.

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