Ammonia electrocatalytic synthesis from nitrate

The interest in electrochemical processes to produce ammonia has increased in recent years. The motivation for this increase is the attempt to reduce the carbon emissions associated with its production, since ammonia is responsible for 1.8% of the global CO2 emissions. Moreover, green ammonia is also seen as a possible transportation fuel in various renewable energy transition scenarios. Several electrochemical processes are being investigated such as N2, NO3–, or NO conversion. Since nitrates are an attractive source of nitrogen, due to their role as water contaminants and facility to break N-O bonds, this mini review is focused on the electrocatalytic synthesis of ammonia from NO3− reduction. Here, we summarized the important work on reaction mechanisms and electrocatalysts for this reaction.</p

Titanium Phosphate Grafted on Mesoporous SBA-15 Silica as a Solid Acid Catalyst for the Synthesis of 5-Hydroxymethylfurfural from Glucose

The grafting of titania on SBA-15 followed by its phosphation was presented to prepare a mesoporous Lewis–Brønsted bifunctional solid acid catalyst for the tandem conversion of glucose via fructose to 5-hydroxymethylfurfural (HMF). Titania was dispersed on SBA-15 as an amorphous surface layer containing abundant coordinatively unsaturated tetrahedral Ti ions, which was reactive and readily transformed upon phosphation into a new titanium phosphate phase with the chemical formula identified as Ti2O3(H2PO4)2·2H2O. The ordered mesoporous structure was well maintained after three modification cycles, affording a desirable surface area of over 300 m2/g. The SBA-15-supported titanium phosphate layer affords higher overall acidity and Brønsted to Lewis acid ratio, compared with the conventional post-phosphated bulk anatase titania. The tetrahedral Ti ions and the adjacent protonated phosphate groups on the titanium phosphate layer could form Lewis–Brønsted acid pairs at molecular level proximity, which largely enhanced the selective tandem catalysis for glucose conversion via fructose to HMF. An optimized HMF yield of 71% was achieved at 160 °C in a water–methyltetrahydrofuran biphasic system over the SBA-15-supported titanium phosphate catalyst. The catalyst exhibited good hydrothermal stability with a rather limited silicon and phosphate leaching, and no distinct pore collapse or performance loss over three sequential reaction runs

Lewis acid-catalyzed depolymerization of soda lignin in supercritical ethanol/water mixtures

The depolymerization of lignin model compounds and soda lignin by super Lewis acidic metal triflates has been investigated in a mixture of ethanol and water at 400 °C. The strong Lewis acids convert representative model compounds for the structure-forming linkages in lignin, namely α-O-4, 5-O-4 (C-O-C ether bridge), and α-1 (methylene bridge). Only the 5-5′ C-C linkage in biphenyl was unaffected under the given reaction conditions. Full conversion of soda lignin was achieved without char formation. Lignin was converted into a wide range of aliphatic and aromatic hydrocarbons. Ethanol was involved in the alkylation of the lignin depolymerization products. These alkylation reactions increased the product yield by inhibiting repolymerization of the products. The resulting organic phase consisted of aliphatic hydrocarbons (paraffins and olefins), aromatic hydrocarbons (extensively alkylated non-oxygenated mono-aromatics, mainly alkylbenzenes as well as mono-aromatic oxygenates, mainly phenolics), condensation products (mainly naphthalenes) and saturated oxygenates (ketones and carboxylic acids). Although complete product analysis was not possible, the data suggest that the dominant fraction of lignin was converted into monomeric units with a small fraction with molecular weights up to 650 g/mol

Structure of palladium nanoparticles under oxidative conditions

Using density functional theory (DFT) and thermodynamic considerations we study the shape and stability of Pd nanoparticles in oxygen-lean and oxygen- rich atmospheres. We find that at very high oxygen coverage cubes exposing (100) faces will form, which are stabilized due to the formation of a Image o/√(5) x √(5)R27° overlayer. The shape of oxygen-covered Pd and Pt nanoparticles is compared in this study

Selective tandem catalysis for the synthesis of 5-hydroxymethylfurfural from glucose over in-situ phosphated titania catalysts: Insights into structure, bi-functionality and performance in flow microreactors

5-Hydroxymethylfurfural (HMF) synthesis from glucose over in-situ phosphated titania catalysts is presented. Phosphates were incorporated into titania framework forming a titanium phosphate surface layer, where the coordinatively unsaturated tetrahedral TiO4 units act as water-tolerant Lewis acid site (LAS) and the adjacent protonated phosphate as Brønsted acid site (BAS), together forming Lewis-Brønsted acid pairs at molecular-level proximity. Glucose turnover and HMF selectivity were enhanced due to the rapid fructose transfer from LAS to the adjacent BAS for its dehydration to HMF, facilitating LAS liberation for another glucose turnover. Reactions in a water-2-methyltetrahydrofuran biphasic system in packed-bed microreactors gave 66% HMF yield (from 1 M glucose at 150 °C), where the HMF space time yield is about two orders of magnitude higher than that in batch and the literature work. Phosphate leaching from the catalyst is rather limited, whereas the catalyst deactivated mainly by humin deposition and could be regenerated by calcination

Graphene as Metal-Free Catalyst for Aqueous Phase Reforming of Ethylene Glycol

[EN] Graphene obtained by pyrolysis of alginate shows in the absence of any metal, catalytic activity towards the decomposition of ethylene glycol into hydrogen and carbon dioxide at 250 8C due to the presence of hydrogenating/dehydrogenating sites. This reaction has interest in the context of valorization of waste waters from cellulose depolymerization and it is typically catalyzed by platinum and other transition metals. In this regard, the use of graphene as metal-free catalyst may have a considerable advantage from the point of sustainability of the catalyst. Based on the influence of the presence of acids and bases and the lack of influence of quenchers of reactive oxygen species, it is proposed that the active sites on the graphene could be frustrated acid-base Lewis pairs acting as dehydrogenating centers. Controls with oxalic acid and glyoxal have shown that if ethylene glycol is converted into these a-dicarbonylic compounds, spontaneous decarboxylation would occur totally (oxalic acid) or in some extent (glyoxal. 30%). In the last case, decarboxylation is also assisted by graphene.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69153-CO2-R1) and Generalitat Valenciana (Prometeo 2013-014) is gratefully acknowledged. I. E.-A. thank to Spanish Ministry of Science for PhD scholarships. This research is partly funded by the EU-JSPS joint initiative through the NOVACAM project.Esteve-Adell, I.; Bakker, N.; Primo Arnau, AM.; Hensen, EJM.; García Gómez, H. (2017). Graphene as Metal-Free Catalyst for Aqueous Phase Reforming of Ethylene Glycol. ChemistrySelect. 2(22):6338-6343. https://doi.org/10.1002/slct.201701138S6338634322

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol:Influence of Reaction Temperature and Feedstock

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (&gt;380 °C). At preferred intermediate temperatures (300-340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin.</p

Environmental economics of lignin derived transport fuels

This paper explores the environmental and economic aspects of fast pyrolytic conversion of lignin, obtained from 2G ethanol plants, to transport fuels for both the marine and automotive markets. Various scenarios are explored, pertaining to aggregation of lignin from several sites, alternative energy carries to replace lignin, transport modalities, and allocation methodology. The results highlight two critical factors that ultimately determine the economic and/or environmental fuel viability. The first factor, the logistics scheme, exhibited the disadvantage of the centralized approach, owing to prohibitively expensive transportation costs of the low energy-dense lignin. Life cycle analysis (LCA) displayed the second critical factor related to alternative energy carrier selection. Natural gas (NG) chosen over additional biomass boosts well-to-wheel greenhouse gas emissions (WTW GHG) to a level incompatible with the reduction targets set by the U.S. renewable fuel standard (RFS). Adversely, the process' economics revealed higher profits vs. fossil energy carrier. (C) 2017 The Author(s). Published by Elsevier Ltd

Supported nickel-rhenium catalysts for selective hydrogenation of methyl esters to alcohols

The addition of Re to Ni on TiO2 yields efficient catalysts for the hydrogenation of acids and esters to alcohols under mild conditions. Rhenium promotes the formation of atomically dispersed and sub-nanometre-sized bimetallic species interacting strongly with the oxide support

Hydrogen Evolution Electrocatalysis with a Molecular Cobalt Bis(alkylimidazole)methane Complex in DMF: a Critical Activity Analysis

[Co(HBMIMPh2)2](BF4)2 (1) [HBMIMPh2=bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane] was investigated for its electrocatalytic hydrogen evolution performance in DMF using voltammetry and during controlled potential/current electrolysis (CPE/CCE) in a novel in-line product detection setup. Performances were benchmarked against three reported molecular cobalt hydrogen evolution reaction (HER) electrocatalysts, [Co(dmgBF2)2(solv)2] (2) (dmgBF2=difluoroboryldimethylglyoximato), [Co(TPP)] (3) (TPP=5,10,15,20-tetraphenylporphyrinato), and [Co(bapbpy)Cl](Cl) (4) [bapbpy=6,6′-bis-(2-aminopyridyl)-2,2′-bipyridine], showing distinct performances differences with 1 being the runner up in H2 evolution during CPE and the best catalyst in terms of overpotential and Faradaic efficiency during CCE. After bulk electrolysis, for all of the complexes, a deposit on the glassy carbon electrode was observed, and post-electrolysis X-ray photoelectron spectroscopy (XPS) analysis of the deposit formed from 1 demonstrated only a minor cobalt contribution (0.23 %), mainly consisting of Co2+. Rinse tests on the deposits derived from 1 and 2 showed that the initially observed distinct activity was (partly) preserved for the deposits. These observations indicate that the molecular design of the complexes dictates the features of the formed deposit and therewith the observed activity