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Formic acid is a valuable chemical derived from biomass, as it has a high hydrogen-storage capacity and appears to be an attractive source of hydrogen for various applications. Hydrogen production via formic acid decomposition is often based on using supported catalysts with Pt-group metal nanoparticles. In the present paper, we show that the decomposition of the acid proceeds more rapidly on single metal atoms (by up to one order of magnitude). These atoms can be obtained by rather simple means through anchoring Pt-group metals onto mesoporous N-functionalized carbon nanofibers. A thorough evaluation of the structure of the active site by aberration-corrected scanning transmission electron microscopy (ac-STEM) in high-angle annular dark field (HAADF) mode, by CO chemisorption, X-ray photoelectron spectroscopy (XPS) and quantum-chemical calculations reveals that the metal atom is coordinated by a pair of pyridinic nitrogen atoms at the edge of graphene sheets. The chelate binding provides an ionic/electron-deficient state of these atoms prevents their aggregation and thereby leads to an excellent stability under the reaction conditions. Catalysts with single atoms have also shown very high selectivity. Evidently, the findings can be extended to hydrogen production from other chemicals and can be helpful for improving other energy-related and environmentally benign catalytic processes.

Single-site heterogeneous catalysis with isolated Pd atoms was reported earlier mainly for oxidation reactions and for Pd catalysts supported on oxide surfaces. In the present work, we show that single Pd atoms on nitrogen-functionalized mesoporous carbon, observed by aberration-corrected scanning transmission electron microscopy (ac STEM), contribute significantly to the catalytic activity for hydrogen production from vapor-phase formic acid decomposition providing an increase by 2-3 times as compared to Pd catalysts supported on nitrogen-free carbon or unsupported Pd powder. Some gain in selectivity was also achieved.According to X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) studies after ex situ reduction in hydrogen at 573 K, these species exist in a

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Formic acid is a widely used commodity chemical. It can be used as a safe, easily handled, and transported source of hydrogen or carbon monoxide for different reactions, including those producing fuels. The review includes historical aspects of formic acid production. It briefly analyzes production based on traditional sources, such as carbon monoxide, methanol, and methane. However, the main emphasis is on the sustainable production of formic acid from biomass and biomass-derived products through hydrolysis and oxidation processes. New strategies of low-temperature synthesis from biomass may lead to the utilization of formic acid for the production of fuel additives, such as methanol; upgraded bio-oil; γ-valerolactone and its derivatives; and synthesis gas used for the Fischer-Tropsch synthesis of hydrocarbons. Some technological aspects are also considered.

Gold nanoparticles of 2-5 nm supported on woven fabrics of activated carbon fibers (ACF) were effective during CO oxidation at room temperature. To obtain a high metal dispersion, Au was deposited on ACF from aqueous solution of ethylenediamine complex [Au(en) 2 ]Cl 3 via ion exchange with protons of surface functional groups. The temperature-programmed decomposition method showed the presence of two main types of functional groups on the ACF surface: the first type was associated with carboxylic groups easily decomposing to CO 2 and the second one corresponded to more stable phenolic groups decomposing to CO. The concentration and the nature of surface functional groups was controlled using HNO 3 pretreatment followed by either calcination in He (300-1273 K) or by iron oxide deposition. The phenolic groups are able to attach Au 3+ ions, leading to the formation of small Au nanoparticles (< 5 nm) after reduction by H 2 . This was confirmed by high-resolution electron microscopy combined with X-ray energy-dispersive analysis. The catalyst with high Au dispersion demonstrated high activity in CO oxidation. The surface carboxylic groups decomposed during interaction with [Au(en) 2 ]Cl 3 solution and reduced Au 3+ to Au 0 , resulting in the formation of bigger (> 9 nm) Au agglomerates after reduction by H 2 . These catalysts demonstrated lower activity as compared to the ones containing mostly small Au nanoparticles. Complete removal of surface functional groups rendered an inert support that would not interact with the Au precursor. The oxidation state of gold in the Au/ACF catalysts was controlled by X-ray photoelectron spectroscopy before and after the reduction in H 2 . The high-temperature reduction in H 2 (673-773 K) was necessary to activate the catalyst, indicating that metallic gold nanoparticles are active during catalytic CO oxidation.  2004 Elsevier Inc. All rights reserved.

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Formation of vanadia species during the calcination of ball milled mixture of V 2 O 5 with TiO 2 was studied by Raman spectroscopy in situ and at ambient conditions. It is found that calcination in air leads to fast (1-3 h) spreading of vanadia over TiO 2 followed by a slower process leading to the formation of a monolayer vanadia. The calcinated catalyst showed higher activity during toluene oxidation than the uncalcinated one, but the selectivity towards C 7 -oxygenated products (benzaldehyde and benzoic acid) remains unchanged. The activity of the catalysts is ascribed to the formation of vanadia species in the monolayer. The details of the parallel-consecutive reaction scheme of toluene oxidation are presented from steady-state and transient kinetics studies. Different oxygen species seem to participate in the deep and partial oxidation of toluene. Coke formation was observed during the reaction presenting an average composition C 2n H 1.1n . The amount of coke on the catalyst was not dependent on the calcination step and the vanadium content in the catalyst. Coke formation was seen to be responsible for the deactivation of the catalyst.