Understanding electrochemical interfaces through comparing experimental and computational charge density-potential curves.

Electrode-electrolyte interfaces play a decisive role in electrochemical charge accumulation and transfer processes. Theoretical modelling of these interfaces is critical to decipher the microscopic details of such phenomena. Different force field-based molecular dynamics protocols are compared here in a view to connect calculated and experimental charge density-potential relationships. Platinum-aqueous electrolyte interfaces are taken as a model. The potential of using experimental charge density-potential curves to transform cell voltage into electrode potential in force-field molecular dynamics simulations, and the need for that purpose of developing simulation protocols that can accurately calculate the double-layer capacitance, are discussed.

Chemically routed interpore molecular diffusion in metal-organic framework thin films.

Transport diffusivity of molecules in a porous solid is constricted by the rate at which molecules move from one pore to the other, along the concentration gradient, i.e. by following Fickian diffusion. In heterogeneous porous materials, i.e. in the presence of pores of different sizes and chemical environments, diffusion rate and directionality remain tricky to estimate and adjust. In such a porous system, we have realized that molecular diffusion direction can be orthogonal to the concentration gradient. To experimentally determine this complex diffusion rate dependency and get insight of the microscopic diffusion pathway, we have designed a model nanoporous structure, metal-organic framework (MOF). In this model two chemically and geometrically distinct pore windows are spatially oriented by an epitaxial, layer-by-layer growth method. The specific design of the nanoporous channels and quantitative mass uptake rate measurements have indicated that the mass uptake is governed by the interpore diffusion along the direction orthogonal to the concentration gradient. This revelation allows chemically carving the nanopores, and accelerating the interpore diffusion and kinetic diffusion selectivity.

Facile water oxidation by dinuclear mixed-valence CoIII/CoII complexes: the role of coordinated water.

Rational design of a catalyst using earth abundant transition metals that can facilitate the smooth O-O bond formation is crucial for developing efficient water oxidation catalysts. The coordination environment around the metal ion of the catalyst plays a pivotal role in this context. We have chosen dinuclear mixed-valence CoIIICoII complexes of the general formula of [CoIIICoII(LH2)2(X)(H2O)] (X = OAc or Cl) which bear a coordinated water molecule in the primary coordination sphere. We anticipated that the water molecule in the primary sphere can take part in the proton coupled electron transfer (PCET) mechanism which can accelerate the facile formation of the O-O bond under strong alkaline conditions (1 M NaOH). To understand the role of the coordinated water molecule we have generated an analogous complex, [CoIIICoII(LH2)2(o-vanillin)] (o-vanillin = 2-hydroxy-3-methoxybenzaldehyde), without coordinated water. Interestingly, we have found that the water coordinated complexes show better oxygen evolution reaction (OER) activity and stability.

Multiplexed optical barcoding of cells via photochemical programming of bioorthogonal host-guest recognition.

Modern chemical and biological studies are undergoing a paradigm shift, where understanding the fate of individual cells, in an apparently homogeneous population, is becoming increasingly important. This has inculcated a growing demand for developing strategies that label individual cells with unique fluorescent signatures or barcodes so that their spatiotemporal trajectories can be mapped in real time. Among various approaches, light-regulated methods employing photocaged fluorophores have received particular attention, owing to their fine spatiotemporal control over labelling. However, their multiplexed use to barcode large numbers of cells for interrogating cellular libraries or complex tissues remains inherently challenging, due to the lack of multiple spectrally distinct photoactivated states in the currently available photocaged fluorophores. We report here an alternative multiplexable strategy based on optically controlled host-guest recognition in the cucurbit[7]uril (CB[7]) system that provides spatial control over the positioning of fluorophores to generate distinct barcodes in 'user-defined' cells. Using a combination of three spectrally distinct CB[7]-conjugated fluorophores and by sequentially performing cycles of photoactivation and fluorophore encoding, we demonstrate 10-color barcoding in microtubule-targeted fixed cells as well as 7-color barcoding in cell surface glycan targeted live MCF7 cells.

Outstanding Broadband (532 nm to 2.2 µm) and Very Efficient Optical Limiting Performance of Some Defect-Engineered Graphenes.

Graphene derivatives and defect-engineered graphenes have attracted the interest of researchers owing to the excellent and tunable properties they exhibit. In this work the optical limiting performance of two defect-engineered boron- and nitrogen-doped reduced graphene oxides is investigated. Both graphenes are found to exhibit exceptional and broadband optical limiting action ranging from 532 to 2200 nm. Their optical limiting efficiency was found to be superior to that of all the other graphene derivatives studied to date, exhibiting a gradually decreasing optical limiting onset, reaching the record low value of ∼0.002 J cm-2 at 2200 nm. The results demonstrate the potential of engineering the defects of such reduced graphene oxides, resulting in very broadband and efficient optical limiting graphene derivatives, showing a promising method to further tailor their optical and optoelectronic properties.

A tetranuclear cobalt(ii) phosphate possessing a D4R core: an efficient water oxidation catalyst.

The reaction of Co(OAc)2·4H2O with a sterically hindered phosphate ester, LH2, afforded a tetranuclear complex, [CoII(L)(CH3CN)]4·5CH3CN (1) [LH2 = 2,6-(diphenylmethyl)-4-isopropyl-phenyl phosphate]. The molecular structure of 1 reveals that it is a tetranuclear assembly where the Co(ii) centers are present in the alternate corners of a cube. The four Co(ii) centers are held together by four di-anionic [L]2- ligands. The fourth coordination site on Co(ii) is taken by an acetonitrile ligand. Changing the Co(ii) precursor from Co(OAc)2·4H2O to Co(NO3)2·6H2O afforded a mononuclear complex [CoII(LH)2(CH3CN)2(MeOH)2](MeOH)2 (2). In 2, the Co(ii) centre is surrounded by two monoanionic [LH]- ligands and a pair of methanol and acetonitrile solvents in a six-coordinate arrangement. 1 has been found to be an efficient catalyst for electrochemical water oxidation under highly basic conditions while the mononuclear analogue, 2, does not respond to electrochemical water oxidation. The tetranuclear catalyst has excellent electrochemical stability and longevity, as established by chronoamperometry and >1000 cycle durability tests under highly alkaline conditions. Excellent current densities of 1 and 10 mA cm-2 were achieved with overpotentials of 354 and 452 mV respectively. The turnover frequency of this catalyst was calculated to be 5.23 s-1 with an excellent faradaic efficiency of 97%, indicating the selective oxygen evolution reaction (OER) occurring with the aid of this catalyst. A mechanistic insight into the higher activity of complex 1 towards the OER compared to that of complex 2 is also provided using density functional theory based calculations.

Interface and defect engineering of hybrid nanostructures toward an efficient HER catalyst.

The hydrogen evolution reaction (HER) plays a key role in hydrogen production for clean energy harvesting. Designing novel efficient and robust electrocatalysts with sufficient active sites and excellent conductivity is one of the key parameters for hydrogen production using water splitting devices. Recently, low-dimensional carbon materials have gained attention as metal-free catalysts for hydrogen production. Such nanostructures need to be engineered to improve their catalytic activity. Here, we designed and synthesized a B and N doped carbon nanostructure (CNS)-hBN heterostructure as an improved HER catalyst. The hBN layers on CNS could provide exposed defects and edges that act as active sites for proton adsorption and reduction. The composition, structure and chemical properties of the B and N doped CNS-hBN heterostructure were tuned to obtain excellent HER activity. Detailed morphological, structural and electrochemical characterization demonstrated that the synergistic effect rising from the interaction between B and N doped CNS and hBN structures contributes to enhance the electrocatalytic performances. To get more insight into the role of defects and doping, we performed density functional theory (DFT) calculations on the CNS-hBN heterostructure.

Graphene-hBN non-van der Waals vertical heterostructures for four- electron oxygen reduction reaction.

A novel vertical non-van der Waals (non-vdW) heterostructure of graphene and hexagonal boron nitride (G/hBN) is realized and its application in direct four-electron oxygen reduction reaction (ORR) in alkaline medium is established. The G/hBN differs from previously demonstrated vdW heterostructures, where it has a chemical bridging between graphene and hBN allowing a direct charge transfer - resulting in high ORR activity. The ORR efficacy of G/hBN is compared with that of graphene-hBN vdW structure and individual layers of graphene and hBN along with that of benchmark platinum/carbon (Pt/C). The ORR activity of G/hBN is found to be on par with Pt/C in terms of current density but with much higher electrochemical stability and methanol tolerance. The onset potential of the G/hBN is found to be improved from 780 mV at a glassy carbon electrode to 930 mV and 940 mV in gold and platinum electrodes, respectively, indicating its substrate-dependent catalytic activity. This opens possibilities of new benchmark catalysts of metals capped with G/hBN atomic layers, where the underneath metal is protected while keeping the activity similar to that of pristine metal. Density functional theory-based calculations are found to be supporting the observed augmented ORR performance of G/hBN.

On the hydrogen evolution reaction activity of graphene-hBN van der Waals heterostructures.

Although graphene technology has reached technology readiness level 9 and hydrogen fuel has been identified as a viable futuristic energy resource, pristine atomic layers such as graphene are found to be inactive towards the hydrogen evolution reaction (HER). Enhancing the intrinsic catalytic activity of a material and increasing its number of active sites by nanostructuring are two strategies in novel catalyst development. Here, electrocatalytically inert graphene (G) and hexagonal boron nitride (hBN) are made active for the HER by forming van der Waals (vdW) heterostructures via vertical stacking. The HER studies are conducted using defect free shear exfoliated graphite and hBN modified glassy carbon electrodes via layer by layer sequential stacking. The G/hBN stacking pattern (AA, AB, and AB') and stacking sequence (G/hBN or hBN/G) have been found to play important roles in the HER activity. Enhancement in the intrinsic activity of graphene by the formation of G/hBN vdW stacks has been further confirmed with thermally reduced graphene oxide and hBN based structures. Tunability in the HER performance of the G/hBN vdW stack is also confirmed via a three-dimensional rGO/hBN electrode. HER active sites in the G/hBN vdW structures are then mapped using density functional theory calculations, and an atomistic interpretation has been identified.