Quantification of the Effect of an External Magnetic Field on Water Oxidation with Cobalt Oxide Anodes.

Here, we quantify the effect of an external magnetic field (ß) on the oxygen evolution reaction (OER) for a cobalt oxide|fluorine-doped tin oxide coated glass (CoOx|FTO) anode. A bespoke apparatus enables us to precisely determine the relationship between magnetic flux density (ß) and OER activity at the surface of a CoOx|FTO anode. The apparatus includes a strong NdFeB magnet (ßmax = 450 ± 1 mT) capable of producing a magnetic field of 371 ± 1 mT at the surface of the anode. The distance between the magnet and the anode surface is controlled by a linear actuator, enabling submillimeter distance positioning of the magnet relative to the anode surface. We couple this apparatus with a finite element analysis magnetic model that was validated by Hall probe measurements to determine the value of ß at the anode surface. At the largest tested magnetic field strength of ß = 371 ± 1 mT, a 4.7% increase in current at 1.5 V vs the normal hydrogen electrode (NHE) and a change in the Tafel slope of 14.5 mV/dec were observed. We demonstrate through a series of OER measurements at sequential values of ß that the enhancement consists of two distinct regions. The possible use of this effect to improve the energy efficiency of commercial water electrolyzers is discussed, and major challenges pertaining to the accurate measurement of the phenomenon are demonstrated.

Direct H2O2 Synthesis, without H2 Gas.

We report here the direct hydrogenation of O2 gas to form hydrogen peroxide (H2O2) using a membrane reactor without H2 gas. Hydrogen is sourced from water, and the reactor is driven by electricity. Hydrogenation chemistry is achieved using a hydrogen-permeable Pd foil that separates an electrolysis chamber that generates reactive H atoms, from a hydrogenation chamber where H atoms react with O2 to form H2O2. Our results show that the concentration of H2O2 can be increased ∼8 times (from 56.5 to 443 mg/L) by optimizing the ratio of methanol-to-water in the chemical chamber, and through catalyst design. We demonstrate that the concentration of H2O2 is acutely sensitive to the H2O2 decomposition rate. This decomposition rate can be minimized by using AuPd alloy catalysts instead of pure Pd. This study presents a new pathway to directly synthesize H2O2 using water electrolysis without ever using H2 gas.

Physical Separation of H2 Activation from Hydrogenation Chemistry Reveals the Specific Role of Secondary Metal Catalysts.

An electrocatalytic palladium membrane reactor (ePMR) uses electricity and water to drive hydrogenation without H2 gas. The device contains a palladium membrane to physically separate the formation of reactive hydrogen atoms from hydrogenation of the unsaturated organic substrate. This separation provides an opportunity to independently measure the hydrogenation reaction at a surface without any competing H2 activation or proton reduction chemistry. We took advantage of this feature to test how different metal catalysts coated on the palladium membrane affect the rates of hydrogenation of C=O and C=C bonds. Hydrogenation occurs at the secondary metal catalyst and not the underlying palladium membrane. These secondary catalysts also serve to accelerate the reaction and draw a higher flux of hydrogen through the membrane. These results reveal insights into hydrogenation chemistry that would be challenging using thermal or electrochemical hydrogenation experiments.

Strain Influences the Hydrogen Evolution Activity and Absorption Capacity of Palladium.

Strain engineering can increase the activity and selectivity of an electrocatalyst. Tensile strain is known to improve the electrocatalytic activity of palladium electrodes for reduction of carbon dioxide or dioxygen, but determining how strain affects the hydrogen evolution reaction (HER) is complicated by the fact that palladium absorbs hydrogen concurrently with HER. We report here a custom electrochemical cell, which applies tensile strain to a flexible working electrode, that enabled us to resolve how tensile strain affects hydrogen absorption and HER activity for a thin film palladium electrocatalyst. When the electrodes were subjected to mechanically-applied tensile strain, the amount of hydrogen that absorbed into the palladium decreased, and HER electrocatalytic activity increased. This study showcases how strain can be used to modulate the hydrogen absorption capacity and HER activity of palladium.

Synthesis and optical and electronic properties of core-modified 21,23-dithiaporphyrins.

Core-modified 21,23-dithiaporphyrins, meso-substituted with both electron-withdrawing 4-phenylcarboxylic acids and related butyl esters, and electron-donating phenyldodecyl ethers were synthesized. The porphyrins displayed broad absorbance profiles that spanned from 400 to 800 nm with molar absorptivities ranging from 2500 to 200000 M(-1) cm(-1). Electrochemical experiments showed the dithiaporphyrins undergo two consecutive, one-electron, quasi-reversible oxidations and reductions at -1.78, -1.43, 0.63, and 0.91 V versus a ferrocene/ferrocenium internal standard. Spectroelectrochemistry and cyclic voltammetry revealed the dithiaporphyrins are stable and can endure many cycles of oxidation and reduction without signs of decomposition. The electronics of the two dithiaporphyrins were similar, and DFT calculations showed the HOMO-LUMO energy difference was smaller than tetrapyrrolic porphyrin analogues. Overall, the combination of desirable electronics, namely: quasi-reversible oxidations and reductions as well as broad absorbance profiles, combined with stability, imply that these core-modified 21,23-dithiaporphyirns could be potentially used as an ambipolar material for organic electronic applications.

Bioelectrocatalysis with a palladium membrane reactor.

Enzyme catalysis is used to generate approximately 50,000 tons of value-added chemical products per year. Nearly a quarter of this production requires a stoichiometric cofactor such as NAD+/NADH. Given that NADH is expensive, it would be beneficial to regenerate it in a way that does not interfere with the enzymatic reaction. Water electrolysis could provide the proton and electron equivalent necessary to electrocatalytically convert NAD+ to NADH. However, this form of electrocatalytic NADH regeneration is challenged by the formation of inactive NAD2 dimers, the use of high overpotentials or mediators, and the long-term electrochemical instability of the enzyme during electrolysis. Here, we show a means of overcoming these challenges by using a bioelectrocatalytic palladium membrane reactor for electrochemical NADH regeneration from NAD+. This achievement is possible because the membrane reactor regenerates NADH through reaction of hydride with NAD+ in a compartment separated from the electrolysis compartment by a hydrogen-permselective Pd membrane. This separation of the enzymatic and electrolytic processes bypasses radical-induced NAD+ degradation and enables the operator to optimize conditions for the enzymatic reaction independent of the water electrolysis. This architecture, which mechanistic studies reveal utilizes hydride sourced from water, provides an opportunity for enzyme catalysis to be driven by clean electricity where the major waste product is oxygen gas.

Electrolysis Can Be Used to Resolve Hydrogenation Pathways at Palladium Surfaces in a Membrane Reactor.

For common hydrogenation chemistries that occur at high temperatures (where H2 is adsorbed and activated at the same surface which the substrate must also adsorb for reaction), there is often little consensus on how the reactions (e.g., hydro(deoxy)genation) actually occur. We demonstrate here that an electrocatalytic palladium membrane reactor (ePMR) can be used to study hydrogenation reaction mechanisms at ambient temperatures, where the catalyst does not necessarily undergo structural reorganization. The ePMR uses electrolysis and a hydrogen-selective palladium membrane to deliver reactive hydrogen to a catalyst surface in an adjacent compartment for reaction with an organic substrate. This process forms the requisite metal-hydride surface for hydrogenation chemistry, but at ambient temperature and pressure, and without a H2 source. We demonstrate the utility of this analytical tool by studying the hydrogenation of benzaldehyde at palladium nanocubes with dimensions of 13-24 nm. This experimental design enabled us to resolve that the alcohol product forms at the facial sites, whereas the hydrodeoxygenation step occurs at edge sites. These observations enabled us to develop the first site-specific definition of how a carbonyl species undergoes hydro(deoxy)genation.

Photoelectrochemical Decomposition of Lignin Model Compound on a BiVO4 Photoanode.

The photoelectrochemical decomposition of lignin model compounds at a BiVO4 photoanode is demonstrated with simulated sunlight and an applied bias of 2.0 V. These prototypical lignin model compounds are photoelectrochemically converted into the corresponding aryl aldehyde and phenol derivatives in a single step with conversion of up to ≈64 % over 20 h. Control experiments suggest that vanadium sites are electrocatalytically active, which precludes the need for a redox mediator in solution. This feature of the system is corroborated by a layer of V2 O5 deposited on BiVO4 serving to boost the conversion by 10 %. Our methodology capitalizes on the reactive power of sunlight to drive reactions that have only been studied previously by electrochemical or catalytic methods. The use of a BiVO4 photoanode to drive lignin model decomposition therefore provides a new platform to extract valuable aromatic chemical feedstocks using solar energy, electricity and biomass as the only inputs.