Mesoporous-rich calcium and potassium-activated carbons prepared from degreased spent coffee grounds for efficient removal of MnO4 2- in aqueous media.

Commercial ACs typically possess high surface areas and high microporosity. However, ACs with appreciable mesoporosity are growing in consideration and demand because they are beneficial for the adsorption of large species, such as heavy metal ions. Thus, in this study, degreased coffee grounds (DCG) were used as precursors for the production of ACs by means of chemical activation at 600 °C for the efficient removal of manganese in the form of MnO4 2-. One of the most common activating agents, ZnCl2, is replaced by benign and sustainable CaCl2 and K2CO3. Three ratios 1 : 1, 1 : 0.5 and 1 : 0.1 of precursor-to-activating agent (g g-1) were investigated. Porosimetry indicates 1 : 1 CaCl2 DCGAC is highly mesoporous (mesopore volume 0.469 cm3 g-1). CaCl2 DCGAC and K2CO3 DCGAC shows high adsorption capacities of 0.494 g g-1 and 0.423 g g-1, respectively for the uptake of MnO4 2- in aqueous media. The adsorption process follows pseudo-second order kinetics inline with the Freundlich isotherm (R 2 > 0.9). Thermodynamic data revealed negative values of ΔG (approx -0.1751 kJ mol-1) demonstrating that the adsorption process on 1 : 1 CaCl2DCGAC was spontaneous.

Biomass composition of the golden tide pelagic seaweeds Sargassum fluitans and S. natans (morphotypes I and VIII) to inform valorisation pathways.

Massive strandings of the pelagic brown algae Sargassum have occurred in the Caribbean, and to a lesser extent, in western Africa, almost every year since 2011. These events have major environmental, health, and economic impacts in the affected countries. Once on the shore, Sargassum is mechanically harvested and disposed of in landfills. Existing commercial applications of other brown algae indicate that the pelagic Sargassum could constitute a valuable feedstock for potential valorisation. However, limited data on the composition of this Sargassum biomass was available to inform on possible application through pyrolysis or enzymatic fractionation of this feedstock. To fill this gap, we conducted a detailed comparative biochemical and elemental analysis of three pelagic Sargassum morphotypes identified so far as forming Atlantic blooms: Sargassum natans I (SnI), S. fluitans III (Sf), and S. natans VIII (SnVIII). Our results showed that SnVIII accumulated a lower quantity of metals and metalloids compared to SnI and Sf, but it contained higher amounts of phenolics and non-cellulosic polysaccharides. SnVIII also had more of the carbon storage compound mannitol. No differences in the content and composition of the cell wall polysaccharide alginate were identified among the three morphotypes. In addition, enzymatic saccharification of SnI produced more sugars compared to SnVIII and Sf. Due to high content of arsenic, the use of pelagic Sargassum is not recommended for nutritional purposes. In addition, low yields of alginate extracted from this biomass, compared with brown algae used for industrial production, limit its use as viable source of commercial alginates. Further work is needed to establish routes for future valorisation of pelagic Sargassum biomass.

Redox-active ligand assisted electrocatalytic water oxidation by a mononuclear cobalt complex.

In this report, the synthesis, characterization and electrocatalytic oxidation of water by a mononuclear cobalt(iii) complex, [CoIII(dpaq)(Cl)]Cl (1) featuring a redox-active pentadentate amidate ligand (H-dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) is reported. Complex 1 has been found to be a stable and homogeneous water oxidation catalyst (WOC) in 0.1 M phosphate buffer (pH 8.0). A series of experiments (rinse test, SEM, EDX spectroscopy) confirm that this complex acts as a molecular electrocatalyst, and not a precursor of CoOx. The electrocatalytic water oxidation proceeds with high faradaic efficiency (81%) and fast rate (85 s-1). Analysis of the electrochemical reaction kinetics by foot-of-the-wave (FOWA) methodology reveals a high turnover frequency of 1.6 × 104 s-1 which is comparable to the best performing Ru-based WOCs.

Design, Synthesis and Photochemical Properties of a Phenalenone-Based pH Sensor: Switchable pH Sensing in Four Detectable Channels.

The synthesis and pH-sensing property of a novel phenalenone-based compound, 9-(4-hydroxyphenylamino)-1-oxo-phenalenone (HPAP), is reported. The newly synthesized compound is capable of functioning as a pH sensor in the region of pH 7 to 12. The sensor can be used as a colorimetric indicator in the transition from pH 10 to pH 11. The sensor is able to function in four detectable channels. All four channels (UV, emission, colorimetric/visible and photoluminescence) have been shown to be reversible, thus implying the reuse of this single-molecule sensor and indicator for several experiments. Mechanistic investigations have been performed by UV, NMR and DFT studies which indicate that a photoinduced electron transfer (PET) based mechanism could be operative. Straightforward and cost-effective application of the sensor in thin-layer chromatography has also been established.

Electrochemical Water Oxidation Catalyzed by an In Situ Generated α-Co(OH)2 Film on Zeolite-Y Surface.

The design and synthesis of an efficient and robust water-oxidation catalyst with inexpensive materials remains an important challenge in the context of artificial photosynthesis. Herein, a simple but unique technique is reported to in situ generate a thin-film of α-Co(OH)2 on the surface of zeolite-Y [hereafter referred to as Y-α-Co(OH)2 ] that acts as an efficient and stable catalyst for electrochemical water oxidation in alkaline medium. Catalyst Y-α-Co(OH)2 is so stable that it retains its catalytic activity even after 2000 cyclic voltammetric cycles of water oxidation. Expectedly, the chemical composition of α-Co(OH)2 on the surface of zeolite-Y remains same as that of parent Y-α-Co(OH)2 after 2000 electrocatalytic cycles. A Tafel slope as low as 59 mV decade-1 in 0.1 m KOH (pH 13) suggests faster oxygen evolution kinetics (overpotential=329 mV; turnover frequency=0.35 mol O2 (mol Co)-1 s-1 at 1 mA cm-2 ) than the existing α-Co(OH)2 -based electrocatalysts operating in alkaline medium.

A Mononuclear Co(II) Coordination Complex Locked in a Confined Space and Acting as an Electrochemical Water-Oxidation Catalyst: A "Ship-in-a-Bottle" Approach.

Preparing efficient and robust water oxidation catalyst (WOC) with inexpensive materials remains a crucial challenge in artificial photosynthesis and for renewable energy. Existing heterogeneous WOCs are mostly metal oxides/hydroxides immobilized on solid supports. Herein we report a newly synthesized and structurally characterized metal-organic hybrid compound [{Co3 (µ3 -OH)(BTB)2(dpe)2} {Co(H2O)4(DMF)2}0.5]n ⋅n H2O(Co-WOC-1) as an effective and stable water-oxidation electrocatalyst in an alkaline medium. In the crystal structure of Co-WOC-1, a mononuclear Co(II) complex {Co(H2O)4(DMF)2}(2+) is encapsulated in the void space of a 3D framework structure and this translationally rigid complex cation is responsible for a remarkable electrocatalytic WO activity, with a catalytic turnover frequency (TOF) of 0.05 s(-1) at an overpotential of 390 mV (vs. NHE) in 0.1 m KOH along with prolonged stability. This host-guest system can be described as a "ship-in-a-bottle", and is a new class of heterogeneous WOC.

Fluorescence signaling systems for sensing Hg(II) ion derived from A2B-corroles.

Selective detection of Hg(II) ions in solution by a series of novel free base bis-(nitrophenyl) corroles (1-4) with general formula A(2)B (where A = nitrophenyl, and B = N,N-dimethylaminophenyl, thienyl, naphthyl and tridecyloxyphenyl group) is described. Among the free base corroles, 4, with a tridecyloxy long chain moiety, has been found to exhibit the highest Hg(II) sensing ability. The detection is based on the fluorescence quenching of the corroles, arising from the combined effect of static (coordination) and dynamic (exciplex formation) factors.