Catalysts2016, 6(9), 130; doi:10.3390/catal6090130 (registering DOI) - published 27 August 2016 Show/Hide Abstract
Abstract: Platinum-based materials are accepted as the suitable electrocatalysts for anodes and cathodes in direct methanol fuel cells (DMFCs). Nonetheless, the increased demand and scarce world reserves of Pt, as well as some technical problems associated with its use, have motivated a wide research focused to design Pd-based catalysts, considering the similar properties between this metal and Pt. In this review, we present the most recent advancements about Pd-based catalysts, considering Pd, Pd alloys with different transition metals and non-carbon supported nanoparticles, as possible electrodes in DMFCs. In the case of the anode, different reported works have highlighted the capacity of these new materials for overcoming the CO poisoning and promote the oxidation of other intermediates generated during the methanol oxidation. Regarding the cathode, the studies have showed more positive onset potentials, as fundamental parameter for determining the mechanism of the oxygen reduction reaction (ORR) and thus, making them able for achieving high efficiencies, with less production of hydrogen peroxide as collateral product. This revision suggests that it is possible to replace the conventional Pt catalysts by Pd-based materials, although several efforts must be made in order to improve their performance in DMFCs.
Catalysts2016, 6(9), 129; doi:10.3390/catal6090129 (registering DOI) - published 26 August 2016 Show/Hide Abstract
Abstract: The β1α1 loop in the tryptophan biosynthetic enzyme indole-3-glycerol phosphate synthase (IGPS) is important for substrate binding, product release and chemical catalysis. IGPS catalyzes the ring closure of the substrate 1-(o-carboxyphenylamine)-1-dexoyribulose 5-phosphate to form indole-3-glycerol phosphate, involving distinct decarboxylation and dehydration steps. The ring closure step is rate-determining in the thermophilic Sulfolobus sulfataricus enzyme (ssIGPS) at high temperatures. The β1α1 loop is especially important in the dehydration step as it houses the general acid Lys53. We propose that loop dynamics are governed by competing interactions on the N- and C-terminal sides of the loop. We had previously shown that disrupting interactions with the N-terminal side of the loop through the N90A substitution decreases catalytic efficiency, slows down the dehydration step and quenches loop dynamics on the picosecond to millisecond timescales. Here, we show that disrupting interactions on the C-terminal side of the loop through the R64A/D65A substitutions likewise decreases catalytic efficiency, slows down the dehydration step and quenches loop dynamics. Interestingly, the triple substitution R64A/D65A/N90A leads to new μs–ms timescale loop dynamics and makes the ring-closure step rate-determining once again. These results are consistent with a model in which the β1α1 loop is maintained in a structurally dynamic state by these competing interactions, which is important for the dehydration step of catalysis. Competing interactions in other enzymes may likewise keep their loops and other structural elements appropriately mobile.
Catalysts2016, 6(9), 128; doi:10.3390/catal6090128 (registering DOI) - published 26 August 2016 Show/Hide Abstract
Abstract: Catalysis fulfills the promise that high-yielding chemical transformations will require little energy and produce no toxic waste. This message is carried by the study of the evolution of molecular catalysis of some of the most important reactions in organic chemistry. After reviewing the conceptual underpinnings of catalysis, we discuss the applications of different catalysts according to the mechanism of the reactions that they catalyze, including acyl group transfers, nucleophilic additions and substitutions, and C–C bond forming reactions that employ umpolung by nucleophilic additions to C=O and C=C double bonds. We highlight the utility of a broad range of organocatalysts other than compounds based on proline, the cinchona alkaloids and binaphthyls, which have been abundantly reviewed elsewhere. The focus is on organocatalysts, although a few examples employing metal complexes and enzymes are also included due to their significance. Classical Brønsted acids have evolved into electrophilic hands, the fingers of which are hydrogen donors (like enzymes) or other electrophilic moieties. Classical Lewis base catalysts have evolved into tridimensional, chiral nucleophiles that are N- (e.g., tertiary amines), P- (e.g., tertiary phosphines) and C-nucleophiles (e.g., N-heterocyclic carbenes). Many efficient organocatalysts bear electrophilic and nucleophilic moieties that interact simultaneously or not with both the electrophilic and nucleophilic reactants. A detailed understanding of the reaction mechanisms permits the design of better catalysts. Their construction represents a molecular science in itself, suggesting that sooner or later chemists will not only imitate Nature but be able to catalyze a much wider range of reactions with high chemo-, regio-, stereo- and enantioselectivity. Man-made organocatalysts are much smaller, cheaper and more stable than enzymes.
Abstract: A comparison between different carbon-based gas-diffusion air-breathing cathodes for microbial fuel cells (MFCs) is presented in this work. A micro-porous layer (MPL) based on carbon black (CB) and an activated carbon (AC) layer were used as catalysts and applied on different supporting materials, including carbon cloth (CC), carbon felt (CF), and stainless steel (SS) forming cathode electrodes for MFCs treating urine. Rotating ring disk electrode (RRDE) analyses were done on CB and AC to: (i) understand the kinetics of the carbonaceous catalysts; (ii) evaluate the hydrogen peroxide production; and (iii) estimate the electron transfer. CB and AC were then used to fabricate electrodes. Half-cell electrochemical analysis, as well as MFCs continuous power performance, have been monitored. Generally, the current generated was higher from the MFCs with AC electrodes compared to the MPL electrodes, showing an increase between 34% and 61% in power with the AC layer comparing to the MPL. When the MPL was used, the supporting material showed a slight effect in the power performance, being that the CF is more powerful than the CC and the SS. These differences also agree with the electrochemical analysis performed. However, the different supporting materials showed a bigger effect in the power density when the AC layer was used, being the SS the most efficient, with a power generation of 65.6 mW·m−2, followed by the CC (54 mW·m−2) and the CF (44 mW·m−2).
Abstract: In the present work, gold complex catalysts with Mor-DalPhos ligands were successfully prepared using mesylates as counter ions. Seven ammonium sulfonates were synthesized to promote the production of intermediate sulfonyloxymethyl ketone. It was found that low-acidity N,N-dimethylbenzenaminium methanesulfonate showed excellent activity in the reaction. Furthermore, the catalysts effectively avoided the loss of activity due to the low acidity. Various thioamides were directly added to the resulting reaction mixture without the separation of intermediate product. Then, twenty kinds of 2,4-disubstituted thiazoles were efficiently synthesized at room temperature with the highest yield of 91%. This work provides an efficiency and mild gold-catalyzed oxidation system for the one-pot synthesis of thiazole and its derivatives.
Abstract: Pt(Cu)/C and Pt-Ru(Cu)/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different species has been modified and the obtained electrocatalysts have been characterized using electrochemical and structural techniques. The High Resolution Transmission Electron Microscopy (HRTEM), Fast Fourier Transform (FFT) and Energy Dispersive X-ray (EDX) microanalyses allowed the determining of the effects of the electrodeposition time on the nanoparticle size and composition. The best conditions identified from Cyclic Voltammetry (CV) corresponded to onset potentials for CO and methanol oxidation on Pt-Ru(Cu)/C of 0.41 and 0.32 V vs. the Reversible Hydrogen Electrode (RHE), respectively, which were smaller by about 0.05 V than those determined for Ru-decorated commercial Pt/C. The CO oxidation peak potentials were about 0.1 V smaller when compared to commercial Pt/C and Pt-Ru/C. The positive effect of Cu was related to its electronic effect on the Pt shells and also to the generation of new active sites for CO oxidation. The synthesis conditions to obtain the best performance for CO and methanol oxidation on the core-shell Pt-Ru(Cu)/C electrocatalysts were identified. When compared to previous results in literature for methanol, ethanol and formic acid oxidation on Pt(Cu)/C catalysts, the present results suggest an additional positive effect of the deposited Ru species due to the introduction of the bifunctional mechanism for CO oxidation.