Synthesis of Upper-Rim Sulfanylpropyl- and p-Methoxyphenylazo-Substituted Calix[4]arenes as Chromogenic Sensors for Hg2+ and Ag+ Ions.

A series of calix[4]arenes with upper-rim sulfanylpropyl and p-methoxyphenylazo groups (compounds 8-10) were synthesized and found to be effective chromogenic sensors for selectively detecting Hg2+, Hg+, and Ag+ ions among 18 screened metal perchlorates. In comparison to previously reported diallyl- and dithioacetoxypropyl-substituted calix[4]arenes (5, 6, 14, 15, and 16) and the newly synthesized compound 7, the distal (5,17)-disulfanylpropyl-substituted di-p-methoxyphenylazocalix[4]arene 9 demonstrated superior performance with a limit of detection of 0.028 µM for Hg2+ ions in a chloroform/methanol (v/v = 399/1) cosolvent. Job's plot revealed 1:1 binding stoichiometry for all these upper-rim sulfanylpropyl- and p-methoxyphenylazo-substituted calix[4]arenes 8-10 with Hg2+ ions, and Benesi-Hildebrand plots from ultraviolet/visible (UV-vis) titration spectra were used for the determination of their association constants. Our findings indicated that the distal orientation of two p-methoxyphenylazo and two sulfanylpropyl groups in calix[4]arenes 8-10 is more favorable for binding Hg2+ ions than the proximal (5,11-) orientation; moreover, the adjacent sulfanylpropyl groups exhibited superior coordination as ligands compared to the allyl and thioacetoxypropyl groups. Notably, compounds 8-10 displayed a comparable trend in their association with Ag+ ions, albeit with 1 order of magnitude lower binding constants and a distinct binding mode compared to Hg2+ ions. UV-vis spectroscopy, Job's plots, high-resolution mass spectrometry, and 1H nuclear magnetic resonance titration studies are presented and discussed.

Potassium-Presenting Zinc Oxide Surfaces Induce Vertical Phase Separation in Fullerene-Free Organic Photovoltaics.

Bulk heterojunction (BHJ) structure based organic photovoltaics (OPVs) have recently showed great potential for achieving high power conversion efficiencies (PCEs). An ideal BHJ structure would feature large donor/acceptor interfacial areas for efficient exciton dissociation and gradient distributions with high donor and acceptor concentrations near the anode and cathode, respectively, for efficient charge extraction. However, the random mixing of donors and acceptors in the BHJ often suffers the severe charge recombination in the interface, resulting in poor charge extraction. Herein, we propose a new approach-treating the surface of the zinc oxide (ZnO) as an electron transport layer with potassium hydroxide-to induce vertical phase separation of an active layer incorporating the nonfullerene acceptor IT-4F. Density functional theory calculations suggested that the binding energy difference between IT-4F and the PBDB-T-2Cl, to the potassium (K)-presenting ZnO interface, is twice as strong as that for IT-4F and PBDB-T-2Cl to the untreated ZnO surface, such that it would induce more IT-4F moving toward the K-presenting ZnO interface than the untreated ZnO interface thermodynamically. Benefiting from efficient charge extraction, the best PCEs increased to 12.8% from 11.8% for PBDB-T-2Cl:IT-4F-based devices, to 12.6% from 11.6% for PBDB-T-2Cl:Y1-4F-based devices, to 13.5% from 12.2% for PBDB-T-2Cl:Y6-based devices, and to 15.7% from 15.1% for PM6:Y6-based devices.

Ni-Nanocluster Modified Black TiO2 with Dual Active Sites for Selective Photocatalytic CO2 Reduction.

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO2 (Ni/TiO2[Vo] ) with built-in dual active sites for selective photocatalytic CO2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored.

Investigation on broadband emission of two-dimensional melamine lead iodide perovskite (2D-C3H8N6PbI4): An experimental and theoretical approach.

Novel two-dimensional melamine lead iodide perovskite (2D-C3H8N6PbI4) is synthesized to investigate its crystallinity, optical band gap and broadband emission properties and to make comparisons with 2D-C3H8N6PbCl4/2D-C3H8N6PbBr4 perovskites. Both experimental and density functional theory (DFT) interrogations on 2D-C3H8N6PbX4 (X = Cl, Br and I) are conducted. The crystal structure, morphology and percentile of Pb and halide elements are confirmed using scanning electron microscope (SEM), and energy dispersive spectrum (EDS), powder/single crystal X-ray diffraction (PXRD/SXRD), DFT and X-ray crystallography simulations. The optical band gaps of 2D-C3H8N6PbX4 perovskites are determined from the Tauc plot fitting of absorbance and DFT studies. Distinct broadband emission of 2D-C3H8N6PbX4 perovskites between 300 and 800 nm is observed, which can be fitted with multiple Gaussian distributions. The fittings of broad PL spectra from 2D-C3H8N6PbCl4/2D-C3H8N6PbBr4 perovskites confirm the involvement of both Dexter energy transfer from melamine cation and self-trapped excitons (STEs). However, the broadband emission of 2D-C3H8N6PbI4 is attributed only to the Dexter energy transfer from melamine cation and the absence of STEs is attributed to the larger lattice deformation of 2D-C3H8N6PbI4. Moreover, the involvement of spin-orbit coupling (SOC) in the energy transfer is clarified to attest that the broadband emission of 2D-C3H8N6PbI4 is distinct among its halide family.

Mimicking Metalloenzyme Microenvironments in the Transition Metal-Single Atom Catalysts for Electrochemical Hydrogen Peroxide Synthesis in an Acidic Medium.

Electrochemical reduction of oxygen into hydrogen peroxide in an acidic medium offers an energy-efficient and green H2 O2 synthesis as an alternative to the energy-intensive anthraquinone process. Unfortunately, high overpotential, low production rates, and fierce competition from traditional four-electron reduction limit it. In this study, a metalloenzyme-like active structure is mimicked in carbon-based single-atom electrocatalysts for oxygen reduction to H2 O2 . Using a carbonization strategy, the primary electronic structure of the metal center with nitrogen and oxygen coordination is modulated, followed by epoxy oxygen functionalities close to the metal active sites. In an acidic medium, CoNOC active structures proceed with greater than 98% H2 O2 selectivity (2e- /2H+ ) rather than CoNC active sites that are selective to H2 O (4e- /4H+ ). Among all MNOC (M = Fe, Co, Mn, and Ni) single-atom electrocatalysts, the CoNOC is the most selective (> 98%) for H2 O2 production, with a mass activity of 10 A g-1 at 0.60 V vs. RHE. X-ray absorption spectroscopy is used to identify the formation of unsymmetrical MNOC active structures. Experimental results are also compared to density functional theory calculations, which revealed that the structure-activity relationship of the epoxy-surrounded CoNOC active structure reaches optimum (ΔG*OOH ) binding energies for high selectivity.

Controlled Sol-Gel and Diversiform Nanostructure Transitions by Photoresponsive Molecular Switching of Tetraphenylethene- and Azobenzene-Functionalized Organogelators.

The implementation of stimuli-responsive materials with dynamically controllable features has long been an important objective that challenges chemists in the materials science field. We report here the synthesis and characterization of [2]rotaxanes (R1 and R1-b) with a molecular shuttle and photoresponsive properties. Axles T1 and T1-b were found to be highly efficient and versatile organogelators toward various nonpolar organic solvents, especially p-xylene, with critical gelation concentrations as low as 0.67 and 0.38 w/v %, respectively. The two molecular stations of switchable [2]rotaxanes (R1 and R1-b) can be revealed or concealed by t-butylcalix[4]arene macrocycle, thus inhibiting the gelation processes of the respective axles T1 and T1-b through the control of intermolecular hydrogen-bonding interactions. The sol-gel transition of axles T1 and T1-b could be achieved by the irradiation of UV-visible light, which interconverted between the extended and contracted forms. Interestingly, the morphologies of organogels in p-xylene, including flakes, nanobelts, fibers, and vesicles depending on the molecular structures of axles T1 and T1-b, were induced by UV-visible light irradiation. Further studies revealed that acid-base-controllable and reversible self-assembled nanostructures of these axle molecules were mainly constructed by the interplay of multi-noncovalent interactions, such as intermolecular π-π stacking, CH-π, and intermolecular hydrogen-bonding interactions. Surprisingly, our TPE molecular systems (R1, R1-b, T1, and T1-b) are nonemissive in their aggregated states, suggesting that not only fluorescence resonance energy transfer but also aggregation-caused quenching may have been functioning. Finally, the mechanical strength of these organogels in various solvents was monitored by rheological experiments.

Development of Novel Mixed Halide/Superhalide Tin-Based Perovskites for Mesoscopic Carbon-Based Solar Cells.

Tin perovskites suffer from poor stability and a self-doping effect. To solve this problem, we synthesized novel tin perovskites based on superhalide with varied ratios of tetrafluoroborate to iodide and implemented them into solar cells based on a mesoscopic carbon-electrode architecture because film formation was an issue in applying this material for a planar heterojunction device structure. We undertook quantum-chemical calculations based on plane-wave density functional theory (DFT) methods and explored the structural and electronic properties of tin perovskites FASnI3-x(BF4)x in the series x = 0, 1, 2, and 3. We found that only the x = 2 case, FASnI(BF4)2, was successfully produced, beyond the standard FASnI3. The electrochemical impedance and X-ray photoelectron spectra indicate that the addition of tin tetrafluoroborate instead of SnI2 suppressed trap-assisted recombination by decreasing the Sn4+ content. The power conversion efficiency of the FASnI(BF4)2 device with FAI and Sn(BF4)2 in an equimolar ratio improved 72% relative to that of a standard FASnI3 solar cell, with satisfactory photostability under ambient air conditions.

Development of Hybrid Pseudohalide Tin Perovskites for Highly Stable Carbon-Electrode Solar Cells.

Tin-based perovskites degrade rapidly upon interaction with water and oxygen in air because Sn-I bonds are weak. To address this issue, we developed novel tin perovskites, FASnI(3-x)(SCN)x (x = 0, 1, 2, or 3), by employing a pseudohalide, thiocyanate (SCN-), as a replacement for halides and as an inhibitor to suppress the Sn2+/Sn4+ oxidation. The structural and electronic properties of pseudohalide tin perovskites in this series were explored with quantum-chemical calculations by employing the plane-wave density functional theory (DFT) method; the corresponding results are consistent with the experimental results. Carbon-based perovskite devices fabricated with tin perovskite FASnI(SCN)2 showed about a threefold enhancement of the device efficiency (2.4%) relative to that of the best FASnI3-based device (0.9%), which we attribute to the improved suppression of the formation of Sn4+, retarded charge recombination, enhanced hydrophobicity, and stronger interactions between Sn and thiocyanate for FASnI(SCN)2 than those for FASnI3. After the incorporation of phenylethyleneammonium iodide (PEAI, 10%) and ethylenediammonium diiodide (EDAI2, 5%) as coadditives, the FASnI(SCN)2 device gave the best photovoltaic performance with JSC = 20.17 mA cm-2, VOC = 322 mV, fill factor (FF) = 0.574, and overall efficiency of power conversion PCE = 3.7%. Moreover, these pseudohalide-containing devices display negligible photocurrent-voltage hysteresis and great stability in ambient air conditions.

KSCN-induced Interfacial Dipole in Black TiO2 for Enhanced Photocatalytic CO2 Reduction.

Tuning the electronic band structure of black titania to improve photocatalytic performance through conventional band engineering methods has been challenging because of the defect-induced charge carrier and trapping sites. In this study, KSCN-modified hydrogenated nickel nanocluster-modified black TiO2 (SCN-H-Ni-TiO2) exhibits enhanced photocatalytic CO2 reduction due to the interfacial dipole effect. Upon combining the experimental and theoretical simulation approach, the presence of an electrostatic interfacial dipole associated with chemisorption of SCN has dramatic effects on the photocatalyst band structure in SCN-H-Ni-TiO2. An interfacial dipole possesses a more negative zeta potential shift of the isoelectric point from 5.20 to 3.20, which will accelerate the charge carrier separation and electron transfer process. Thiocyanate ion passivation on black TiO2 demonstrated an increased work function around 0.60 eV, which was induced by the interracial dipole effect. Overall, the SCN-H-Ni-TiO2 photocatalyst showed an enhanced CO2 reduction to solar fuel yield by 2.80 times higher than H-Ni-TiO2 and retained around 88% product formation yield after 40 h.

Symmetry and coplanarity of organic molecules affect their packing and photovoltaic properties in solution-processed solar cells.

In this study we synthesized three acceptor-donor-acceptor (A-D-A) organic molecules, TB3t-BT, TB3t-BTT, and TB3t-BDT, comprising 2,2'-bithiophene (BT), benzo[1,2-b:3,4-b':5,6-d″]trithiophene (BTT), and benzo[1,2-b;4,5-b']dithiophene (BDT) units, respectively, as central cores (donors), terthiophene (3t) as π-conjugated spacers, and thiobarbituric acid (TB) units as acceptors. These molecules display different degrees of coplanarity as evidenced by the differences in dihedral angles calculated from density functional theory. By using differential scanning calorimetry and X-ray diffractions for probing their crystallization characteristics and molecular packing in active layers, we found that the symmetry and coplanarity of molecules would significantly affect the melting/crystallization behavior and the formation of crystalline domains in the blend film with fullerene, PC61BM. TB3t-BT and TB3t-BDT, which each possess an inversion center and display high crystallinity in their pristine state, but they have different driving forces in crystallization, presumably because of different degrees of coplanarity. On the other hand, the asymmetrical TB3t-BTT behaved as an amorphous material even though it possesses a coplanar structure. Among our tested systems, the device comprising as-spun TB3t-BDT/PC61BM (6:4, w/w) active layer featured crystalline domains and displayed the highest power conversion efficiency (PCE) of 4.1%. In contrast, the as-spun TB3t-BT/PC61BM (6:4, w/w) active layer showed well-mixed morphology and with a device PCE of 0.2%; it increased to 3.9% after annealing the active layer at 150 °C for 15 min. As for TB3t-BTT, it required a higher content of fullerene in the TB3t-BTT/PC61BM (4:6, w/w) active layer to optimize its device PCE to 1.6%.