Artificial photosynthesis and the splitting of water to generate hydrogen

It is no exaggeration to state that the energy crisis is the most serious challenge that we face today. Among the strategies to gain access to reliable, renewable energy, the use of solar energy has clearly emerged as the most viable option. A promising direction in this context is artificial photosynthesis. In this article, we briefly describe the essential features of artificial photosynthesis in comparison with natural photosynthesis and point out the modest success that we have had in splitting water to produce oxygen and hydrogen, specially the latter.

Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study

Using van-der-Waals-corrected density functional theory calculations, we explore the possibility of engineering the local structure and morphology of high-surface-area graphene-derived materials to improve the uptake of methane and carbon dioxide for gas storage and sensing. We test the sensitivity of the gas adsorption energy to the introduction of native point defects, curvature, and the application of strain. The binding energy at topological point defect sites is inversely correlated with the number of missing carbon atoms, causing Stone-Wales defects to show the largest enhancement with respect to pristine graphene (similar to 20%). Improvements of similar magnitude are observed at concavely curved surfaces in buckled graphene sheets under compressive strain, whereas tensile strain tends to weaken gas binding. Trends for CO2 and CH4 are, similar, although CO2 binding is generally stronger by similar to 4 to 5 kJ mol(-1). However, the differential between the adsorption of CO2 and CH4 is much higher on folded graphene sheets and at concave curvatures; this could possibly be leveraged for CH4/CO2 flow separation and gasselective sensors.

Designing Ternary Co-crystals with Stacking Interactions and Weak Hydrogen Bonds. 4,4 `-Bis-hydroxyazobenzene

Three ternary co-crystals of the title compound are reported. The design strategy hinges on the identification of a robust synthon with O-H center dot center dot center dot N hydrogen bonds in a binary co-crystal. Construction of this module allows the tuning of pi center dot center dot center dot pi stacking interactions and weak hydrogen bonds to incorporate the third component into the crystal structure. Screening of various co-formers showed that a delicate balance of electrostatics is required for stacking to favor the formation of ternaries. A C-H center dot center dot center dot N hydrogen-bonded motif was also found to occur repetitively in the ternary co-crystals. The directional nature of weak hydrogen bonds allows them to be used effectively in this study.

Effect of quantum nuclear motion on hydrogen bonding

This work considers how the properties of hydrogen bonded complexes, X-H center dot center dot center dot Y, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (X) and acceptor (Y) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H center dot center dot center dot O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4-3.0 angstrom, i.e., from strong to weak hydrogen bonds. The position of the proton (which determines the X-H bond length) and its longitudinal vibrational frequency, along with the isotope effects in both are described quantitatively. An analysis of the secondary geometric isotope effect, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of bending modes is also considered: their quantum effects compete with those of the stretching mode for weak to moderate H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several trends. (C) 2014 AIP Publishing LLC.

A Modified Fluorimetric Method for Determination of Hydrogen Peroxide Using Homovanillic Acid Oxidation Principle

Hydrogen peroxide (H2O2) level in biological samples is used as an important index in various studies. Quantification of H2O2 level in tissue fractions in presence of H2O2 metabolizing enzymes may always provide an incorrect result. A modification is proposed for the spectrofluorimetric determination of H2O2 in homovanillic acid (HVA) oxidation method. The modification was included to precipitate biological samples with cold trichloroacetic acid (TCA, 5% w/v) followed by its neutralization with K2HPO4 before the fluorimetric estimation of H2O2 is performed. TCA was used to precipitate the protein portions contained in the tissue fractions. After employing the above modification, it was observed that H2O2 content in tissue samples was >= 2 fold higher than the content observed in unmodified method. Minimum 2 h incubation of samples in reaction mixture was required for completion of the reaction. The stability of the HVA dimer as reaction product was found to be > 12 h. The method was validated by using known concentrations of H2O2 and catalase enzyme that quenches H2O2 as substrate. This method can be used efficiently to determine more accurate tissue H2O2 level without using internal standard and multiple samples can be processed at a time with additional low cost reagents such as TCA and K2HPO4.

Enhancing hydrogen storage capacity of pyridine-based metal organic framework

Using first principles calculations, we show that the storage capacity as well as desorption temperature of MOFs can be significantly enhanced by decorating pyridine (a common linker in MOFs) by metal atoms. The storage capacity of metal-pyridine complexes are found to be dependent on the type of decorating metal atom. Among the 3d transition metal atoms, Sc turns out to be the most efficient storing unto four H-2 molecules. Most importantly, Sc does not suffer dimerisation on the surface of pyridine, keeping the storage capacity of every metal atom intact. Based on these findings, we propose a metal-decorated pyridine-based MOFs, which has potential to meet the required H-2 storage capacity for vehicular usage. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Estimation of the 2.0(5) helix type i -> i hydrogen bond energy at Aib*-Oxa motif: an isodesmic approach

Bending at the valence angle N-C-alpha-C' (tau) is a known control feature for attenuating the stability of the rare intramolecular hydrogen bonded pseudo five-membered ring C-5 structures, the so called 2.0(5) helices, at Aib. The competitive 3(10)-helical structures still predominate over the C5 structures at Aib for most values of tau. However at Aib*, a mimic of Aib where the carbonyl 0 of Aib is replaced with an imidate N (in 5,6-dihydro-4H-1,3-oxazine = Oxa), in the peptidomimic Piv-Pro-Aib*-Oxa (1), the C(5)i structure is persistent in both crystals and in solution. Here we show that the i -> i hydrogen bond energy is a more determinant control for the relative stability of the C5 structure and estimate its value to be 18.5 +/- 0.7 kJ/mol at Aib* in 1, through the computational isodesmic reaction approach, using two independent sets of theoretical isodesmic reactions. (C) 2014 Elsevier Ltd. All rights reserved.

Hydrogen-Bond-Driven Controlled Molecular Marriage in Covalent Cages

A supramolecular approach that uses hydrogen-bonding interaction as a driving force to accomplish exceptional self-sorting in the formation of imine-based covalent organic cages is discussed. Utilizing the dynamic covalent chemistry approach from three geometrically similar dialdehydes (A, B, and D) and the flexible triamine tris(2-aminoethyl)amine (X), three new 3+2] self-assembled nanoscopic organic cages have been synthesized and fully characterized by various techniques. When a complex mixture of the dialdehydes and triamine X was subjected to reaction, it was found that only dialdehyde B (which has OH groups for H-bonding) reacted to form the corresponding cage B3X2 selectively. Surprisingly, the same reaction in the absence of aldehyde B yielded a mixture of products. Theoretical and experimental investigations are in complete agreement that the presence of the hydroxyl moiety adjacent to the aldehyde functionality in B is responsible for the selective formation of cage B3X2 from a complex reaction mixture. This spectacular selection was further analyzed by transforming a nonpreferred (non-hydroxy) cage into a preferred (hydroxy) cage B3X2 by treating the former with aldehyde B. The role of the H-bond in partner selection in a mixture of two dialdehydes and two amines has also been established. Moreover, an example of unconventional imine bond metathesis in organic cage-to-cage transformation is reported.

Equiatomic ternary chalcogenide: PdPS and its reduced graphene oxide composite for efficient electrocatalytic hydrogen evolution

The layered ternary chalcogenide, palladium phosphorous sulphide (PdPS), and its composite with reduced graphene oxide are shown to be efficient hydrogen evolution electrocatalysts. The Tafel slope and the exchange current density values associated with hydrogen evolution reaction are determined to be 46 mV dec(-1) and 1.4 x 10(-4) A cm(-2) respectively.

Effect of adsorbate loading on selectivity during adsorption of C/C and C/C n-alkane binary mixtures in silicalite

Adsorption experiments of mixtures of long chain alkanes into silicalite under liquid phase conditions show selectivity inversion and azeotrope formation. These effects are due to the subtle interplay between the size of the adsorbed molecules and pore topology of the adsorbent. In this study, the selective uptake of lighter component during liquid phase adsorption of C/C and C/C n-alkane binary mixtures in the zeolite silicalite is understood through configurational bias grand-canonical Monte Carlo molecular simulation technique and a coarse-grained siting analysis. The simulations are conducted under conditions of low and intermediate levels of loading. The siting pattern of the adsorbates inside the zeolite pores explain the selectivity as seen in experiments.

Tautomeric Preference and Conformation Locking in Fenobam, Thiofenobam, and Their Analogues: The Decisive Role of Hydrogen Bond Hierarchy

The crystal and molecular structures of the potential antidepressant drug fenobam and its derivatives are examined in terms of the preferred form among the two possible tautomeric structures. In this study, chemical derivatization has been utilized as a means to ``experimentally simulate'' the tautomeric preference and conformational variability in fenobam. Eight new derivatives of fenobam have been synthesized, and structural features have been characterized by single-crystal X-ray diffraction and NMR spectroscopy. The specific tautomeric preference found in all of these compounds and their known crystal forms have been construed in terms of the stabilizing intramolecular N-H center dot center dot center dot O and N-H center dot center dot center dot S hydrogen bonding. The hierarchy of intramolecular hydrogen bonds evidenced as the preference of the C-H center dot center dot center dot O hydrogen bond over C-H center dot center dot center dot N and that of the C-H center dot center dot center dot N hydrogen bond over C-H center dot center dot center dot S explains the two distinct conformations adopted by fenobam and thiofenobam derivatives. The relative energy values of different molecular conformations have been calculated and compared.

Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different

CONSPECTUS: The halogen bond is an attractive interaction in which an electrophilic halogen atom approaches a negatively polarized species. Short halogen atom contacts in crystals have been known for around 50 years. Such contacts are found in two varieties: type I, which is symmetrical, and type II, which is bent. Both are influenced by geometric and chemical considerations. Our research group has been using halogen atom interactions as design elements in crystal engineering, for nearly 30 years. These interactions include halogen center dot center dot center dot halogen interactions (X center dot center dot center dot X) and halogen center dot center dot center dot heteroatom interactions (X center dot center dot center dot B). Many X center dot center dot center dot X and almost all X center dot center dot center dot B contacts can be classified as halogen bonds. In this Account, we illustrate examples of crystal engineering where one can build up from previous knowledge with a focus that is provided by the modern definition of the halogen bond. We also comment on the similarities and differences between halogen bonds and hydrogen bonds. These interactions are similar because the protagonist atoms halogen and hydrogen are both electrophilic in nature. The interactions are distinctive because the size of a halogen atom is of consequence when compared with the atomic sizes of, for example, C, N, and O, unlike that of a hydrogen atom. Conclusions may be drawn pertaining to the nature of X center dot center dot center dot X interactions from the Cambridge Structural Database (CSD). There is a clear geometric and chemical distinction between type I and type II, with only type II being halogen bonds. Cl/Br isostructurality is explained based on a geometric model. In parallel, experimental studies on 3,4-dichlorophenol and its congeners shed light on the nature of halogen center dot center dot center dot halogen interactions and reveal the chemical difference between Cl and Br. Variable temperature studies also show differences between type I and type II contacts. In terms of crystal design, halogen bonds offer a unique opportunity in the strength, atom size and interaction gradation; this may be used in the design of ternary cocrystals. Structural modularity in which an entire crystal structure is defined as a combination of modules is rationalized on the basis of the intermediate strength of a halogen bond. The specific directionality of the halogen bond makes it a good tool to achieve orthogonality in molecular crystals. Mechanical properties can be tuned systematically by varying these orthogonally oriented halogen center dot center dot center dot halogen interactions. In a further development, halogen bonds are shown to play a systematic role in organization of LSAMs (long range synthon aufbau module), which are bigger structural units containing multiple synthons. With a formal definition in place, this may be the right time to look at differences between halogen bonds and hydrogen bonds and exploit them in more subtle ways in crystal engineering.

Adsorption study of silica gel particle for improvement in design of adsorption beds used in solar driven cooling units

Simulations using Ansys Fluent 6.3.26 have been performed to look into the adsorption characteristics of a single silica gel particle exposed to saturated humid air streams at Re=108 & 216 and temperature of 300K. The adsorption of the particle has been modeled as a source term in the species and the energy equations using a Linear Driving Force (LDF) equation. The interdependence of the thermal and the water vapor concentration field has been analysed. This work is intended to aid in understanding the adsorption effects in silica gel beds and in their efficient design. (C) 2013 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

Solar driven Adsorption Desalination system

Desalination is one of the most traditional processes to generate potable water. With the rise in demand for potable water and paucity of fresh water resources, this process has gained special importance. Conventional thermal desalination processes involves evaporative methods such as multi-stage flash and solar distils, which are found to be energy intensive, whereas reverse osmosis based systems have high operating and maintenance costs. The present work describes the Adsorption Desalination (AD) system, which is an emerging process of thermal desalination cum refrigeration capable of utilizing low grade heat easily obtainable from even non-concentrating type solar collectors. The system employs a combination of flash evaporation and thermal compression to generate cooling and desalinated water. The current study analyses the system dynamics of a 4-bed single stage silica-gel plus water based AD system. A lumped model is developed using conservation of energy and mass coupled with the kinetics of adsorption/desorption process. The constitutive equations for the system components viz. evaporator, adsorber and condenser, are solved and the performance of the system is evaluated for a single stage AD system at various condenser temperatures and cycle times to determine optimum operating conditions required for desalination and cooling. (C) 2013 P. Dutta. Published by Elsevier Ltd.

Effect of hydrogen on the yielding behavior and shear transformation zone volume in metallic glass ribbons

The effect of hydrogen (H) charging on the shear yield strength (tau(max)) and shear transformation zone volume (Omega) of Ni-Nb-Zr metallic glass ribbons, with varying Zr content, were studied through the first pop-in loads during nanoindentation. Weight gain measurements after H charging and desorption studies were utilized to identify how the total H absorbed during charging is partitioned into mobile and immobile (or trapped) parts. These, in turn, indicate the significant role of H mobility in the amorphous structure on the yielding behavior. In high-Zr alloys, tau(max) increases significantly whereas Omega decreases. In low-Zr alloys, a slight decrease in tau(max) and increase in Omega were noted. These experimental observations are rationalized in terms of the mobility of the absorbed H in the amorphous structure and the possible role of it in the shear transformation zone dynamics during deformation of the metallic glass. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.