Pretreatment of Miscanthus giganteus with Lime and Oxidants for Biofuels

ACKNOWLEDEGMENTS The authors are grateful to the Energy Biosciences Institute, University of California, Berkeley, Berkeley, CA, for financial support, Dr. Stefan R. Bauer, Valerie D. Mitchell, and Ana Belen Ibanez Zamora for technical assistance, and Jason Cai for fruitful discussions. The authors thank the China Scholarship Council for financial assistance to Fuxin Yang during his stay at University of California, Berkeley.Peer reviewedPostprin

Production of C-2/C-3 Oxygenates from Planar Copper Nitride-Derived Mesoporous Copper via Electrochemical Reduction of CO2

Electrochemical reduction of CO2 provides an opportunity to produce fuels and chemicals in a carbon-neutral manner, assuming that CO2 can be captured from the atmosphere. To do so requires efficient, selective, and stable catalysts. In this study, we report a highly mesoporous metallic Cu catalyst prepared by electrochemical reduction of thermally nitrided Cu foil. Under aqueous saturated CO2 reduction conditions, the Cu3N-derived Cu electrocatalyst produces virtually no CH4, very little CO, and exhibits a faradaic efficiency of 68% in C2+ products (C2H4, C2H5OH, and C3H7OH) at a current density of ∼18.5 mA cm-2 and a cathode potential of -1.0 V versus the reversible hydrogen electrode. Under these conditions, the catalyst produces more oxygenated products than hydrocarbons. We show that surface roughness is a good descriptor of catalytic performance. The roughest surface reached 98% CO utilization efficiency for C2+ product formation from CO2 reduction and the ratio of oxygenated to hydrocarbon products correlates with the degree of surface roughness. These effects of surface roughness are attributed to the high population of undercoordinated sites as well as a high pH environment within the mesopores and adjacent to the surface of the catalyst

Effects of Surface Roughness on the Electrochemical Reduction of CO₂ over Cu

We have investigated the role of surface roughening on the CO₂ reduction reaction (CO₂RR) over Cu. The activity and product selectivity of Cu surfaces roughened by plasma pretreatment in Ar, O₂, or N₂ were compared with that of electrochemically polished Cu samples. Differences in total and product current densities, the ratio of current densities for HER (the hydrogen evolution reaction) to CO₂RR, and the ratio of current densities for C₂₊ to C₁ products depend on the electrochemically active surface and are nearly independent of plasma composition. Theoretical analysis of an electropolished and roughened Cu surface reveals a higher fraction of undercoordinated Cu sites on the roughened surface, sites that bind CO preferentially. Roughened surfaces also contain square sites similar to those on a Cu(100) surface but with neighboring step sites, which adsorb OC–COH, a precursor to C₂₊ products. These findings explain the increases in the formation of oxygenates and hydrocarbons relative to CO and the ratio of oxygenates to hydrocarbons observed with increasing surface roughness

Understanding brønsted-acid catalyzed monomolecular reactions of Alkanes in Zeolite Pores by combining insights from experiment and theory

Acidic zeolites are effective catalysts for the cracking of large hydrocarbon molecules into lower molecular weight products required for transportation fuels. However, the ways in which the zeolite structure affects the catalytic activity at BrOnsted protons are not fully understood. One way to characterize the influence of the zeolite structure on the catalysis is to study alkane cracking and dehydrogenation at very low conversion, conditions for which the kinetics are well defined. To understand the effects of zeolite structure on the measured rate coefficient (k(app)), it is necessary to identify the equilibrium constant for adsorption into the reactant state (Kads-H+) and the intrinsic rate coefficient of the reaction (k(int)) at reaction temperatures, since k(app) is proportional to the product of Kads-H+ and k(int). We show that Kads-H+ cannot be calculated from experimental adsorption data collected near ambient temperature, but can, however, be estimated accurately from configurational-bias Monte Carlo (CBMC) simulations. Using monomolecular cracking and dehydrogenation of C-3-C-6 alkanes as an example, we review recent efforts aimed at elucidating the influence of the acid site location and the zeolite framework structure on the observed values of k(app) and its components, Kads-H+ and k(int)

Synthesis of Biomass-Derived Ethers for Use as Fuels and Lubricants.

Ethers synthesized from biomass-derived compounds have exceptional properties as fuels, lubricants, and specialty chemicals and can serve as replacements for petroleum-derived products. Recent efforts have identified heterogeneous catalysts for the selective synthesis of ethers from alcohols, aldehydes, ketones, furans, esters, olefins, carboxylic acids, and other molecules derived from biomass. This Review highlights the scope of etherification reactions and provides insights into the choice of catalysts and reaction conditions best suited for producing targeted ethers from the available starting materials. First, the properties of ethers for specific applications and the methods by which synthons for ether synthesis can be obtained from biomass are discussed. Then the progress that has been made on the synthesis of ethers via the following methods is summarized: direct etherification of alcohols; reductive etherification of alcohols with aldehydes or ketones; etherification of furanic compounds, esters, and carboxylic acids; and the addition of alcohols to olefins. Next, the mechanisms of these reactions and catalyst properties required to promote them are discussed, with the goal of understanding how reaction conditions can be tuned to optimize catalyst activity and selectivity towards desired ethers. The Review closes by examining the tradeoffs between catalyst selectivity, activity, stability, and reaction conditions required to achieve the most economically and environmentally favorable routes to biomass-derived ethers

Direct Sulfonation of Methane at Low Pressure to Methanesulfonic Acid in the Presence of Potassium Peroxydiphosphate as the Initiator

Abstract: A high-yield, direct sulfonation of methane with SO 3 to methanesulfonic acid (MSA) is effected in sulfuric acid using potassium peroxydiphosphate (K 4 P 2 O 8 ) as the initiator. The influences of initiator concentration, temperature, CH 4 pressure, the initial concentration of SO 3 , and solvent acidity were investigated. A mechanism is proposed to explain the observed effects of reaction conditions on the conversion of SO 3 to MSA

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Finally, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface

Response to "Impact of Zeolite Structure on Entropic-Enthalpic Contributions to Alkane Monomolecular Cracking: An IR Operando Study".

This is a response to the paper published by S. A. Kadam, H. Li, R. F. Wormsbacher, A. Travert, Chem. Eur. J. 2018, 24, 5489. Key consistencies between our reported results and those reported in this work are also highlighted

Effects of Lewis Acid Catalysts on the Hydrogenation and Cracking of Two-Ring Aromatic and Hydroaromatic Structures Related to Coal

An investigation was carried out of the hydrogenation and cracking of two-ring aromatic and hydroaromatic compounds catalyzed by ZnCl{sub 2} and AlCl{sub 3}. The rates of both processes are strongly affected by the Bronsted acidity of the active catalyst [e.g., H{sup +}(MX{sub n}Y){sup -}] and the Bronsted basicity of the aromatic portions of the reactant, the latter characteristic being enhanced by either methyl or hydroxyl substitution. The source of hydrogen used for hydrogenation depends on the choice of catalyst. In the presence of AlCl{sub 3}, Scholl condensation of aromatic nuclei serves as the principle source of hydrogen. Molecular hydrogen is used exclusively, though, when hydrogenation is catalyzed by ZnCl{sub 2}. The formation of reaction products and the trends in reactant reactivity are discussed on the basis of carbonium ion mechanisms