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The development of earth-abundant catalysts for the oxygen evolution reaction (OER) in acidic media represents a significant challenge in the context of polymer electrolyte membrane (PEM)-based ele...

With the rising emphasis on renewable energy research, the field of electrocatalytic CO2 conversion to fuels has grown tremendously in recent years. Advances in nanomaterial synthesis and characterization have enabled researchers to screen effects of elemental composition, size, and surface chemistry on catalyst performance. However, direct links from structure and active state to catalytic function are difficult to establish. To this end, operando spectroscopic techniques, those conducted simultaneously as catalysts operate, can provide key complementary information by investigating electrocatalysis under turnover conditions. In particular, Raman and infrared spectroscopy have the potential to reveal the identity of surface-bound intermediates, catalyst active state, and possible reaction sites to supplement the insights extracted from conventional electrochemistry. Such research aims to work in tandem synthetic and catalytic efforts to guide the development of next-generation CO2 electrocatalytic system...

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O4 sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry., The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control.

© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. Hydrogenases (H2ases) are benchmark electrocatalysts for H2 production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p-type Si photocathode for optimal loading and wiring of H2ase through the introduction of a hierarchical inverse opal (IO) TiO2 interlayer. This proton-reducing Si|IO-TiO2|H2ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias-free) water splitting by wiring Si|IO-TiO2|H2ase to a modified BiVO4 photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO-TiO2|H2ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z-scheme that replaces the non-complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode.

The electrochemical oxidation of biomass platforms such as 5-hydroxymethylfurfural (HMF) to value-added chemicals is an emerging clean energy technology. However, mechanistic knowledge of this reaction in an electrochemical context is still lacking and operando studies are even more rare. In this work, we utilize core-shell gold-metal oxide nanostructures which enable operando surface-enhanced Raman spectroelectrochemical studies to simultaneously visualize catalyst material transformation and surface reaction intermediates under an applied voltage. As a case study, we show how the transformation of NiOOH from ∼1-2 nm amorphous Ni layers facilitates the onset of HMF oxidation to 2,5-furandicarboxylic acid (FDCA), which is attained with 99% faradaic efficiency in 1 M KOH. In contrast to the case in 1 M KOH, NiOOH formation is suppressed, and consequently HMF oxidation is sluggish in 10 mM KOH, even at highly oxidizing potentials. Operando Raman experiments elucidate how surface adsorption and interaction dictates product selectivity and how the surface intermediates evolve with applied potential. We further extend our methodology to investigate NiFe, Co, Fe, and CoFe catalysts and demonstrate that high water oxidation activity is not necessarily correlated with excellent HMF oxidation performance and highlight catalytic factors important for this reaction such as reactant-surface interactions and the catalysts' physical and electronic structure. The insights extracted are expected to pave the way for a deepened understanding of a wide array of electrochemical systems such as for organic transformations and CO2 fixation.

Liquid phase exfoliation (LPE) of layered compounds towards few- or monolayers has been established as one of the prime methods in the growing field of 2D material research. Here, we present first steps towards an effective LPE of bismuth(iii) iodide, a semiconductor with potential as a photovoltaic absorber material. We highlight guidelines in the choice of exfoliating solvent, which differ significantly from those used with transition metal dichalcogenides or graphene. We also present first evidence of successful few-layer formation from spectroscopic, electron microscopy and electron diffraction investigations.

Semiartificial photosynthesis integrates photosynthetic enzymes with artificial electronics, which is an emerging approach to reroute the natural photoelectrogenetic pathways for sustainable fuel and chemical synthesis. However, the reduced catalytic activity of enzymes in bioelectrodes limits the overall performance and further applications in fuel production. Here, we show new insights into factors that affect the photoelectrogenesis in a model system consisting of photosystem II and three-dimensional indium tin oxide and graphene electrodes. Confocal fluorescence microscopy and in situ surface-sensitive infrared spectroscopy are employed to probe the enzyme distribution and penetration within electrode scaffolds of different structures, which is further correlated with protein film-photoelectrochemistry to establish relationships between the electrode architecture and enzyme activity. We find that the hierarchical structure of electrodes mainly influences the protein loading but not the enzyme activity. Photoactivity is more limited by light intensity and electronic communication at the biointerface. This study provides guidelines for maximizing the performance of semiartificial photosynthesis and also presents a set of methodologies to probe the photoactive biofilms in three-dimensional electrodes.

A critical challenge in energy research is the development of earth abundant and cost-effective materials that catalyze the electrochemical splitting of water into hydrogen and oxygen at high rates and low overpotentials. Key to addressing this issue lies not only in the synthesis of new materials, but also in the elucidation of their active sites, their structure under operating conditions and ultimately, extraction of the structure-function relationships used to spearhead the next generation of catalyst development. In this work, we present a complete cycle of synthesis, operando characterization, and redesign of an amorphous cobalt phosphide (CoP x ) bifunctional catalyst. The research was driven by integrated electrochemical analysis, Raman spectroscopy and gravimetric measurements utilizing a novel quartz crystal microbalance spectroelectrochemical cell to uncover the catalytically active species of amorphous CoP x and subsequently modify the material to enhance the activity of the elucidated catalytic phases. Illustrating the power of our approach, the second generation cobalt-iron phosphide (CoFePx) catalyst, developed through an iteration of the operando measurement directed optimization cycle, is superior in both hydrogen and oxygen evolution reactivity over the previous material and is capable of overall water electrolysis at a current density of 10 mA cm-2 with 1.5 V applied bias in 1 M KOH electrolyte solution.

Surface-enhanced infrared absorption spectroscopy is used in situ to determine the electrochemical stability of organic interfaces deposited onto the surface of nanostructured, thin-film gold electrodes via the electrochemical reduction of diazonium salts. These interfaces are shown to exhibit a wide electrochemical stability window in both acetonitrile and phosphate buffer, far surpassing the stability window of thiol-derived self-assembled monolayers. Using the same in situ technique, the application of radical scavengers during the electrochemical reduction of diazonium salts is shown to moderate interface formation. Consequently, the heterogeneous charge-transfer resistance can be reduced sufficiently to enhance the direct electron transfer between an immobilized redox-active enzyme and the electrode. This was demonstrated for the oxygen-tolerant [NiFe] hydrogenase from the “Knallgas” bacterium Ralstonia eutropha by relating its electrochemical activity for hydrogen oxidation to the interface properties.

Protein immobilization on electrodes is a key concept in exploiting enzymatic processes for bioelectronic devices. For optimum performance, an in-depth understanding of the enzyme-surface interactions is required. Here, we introduce an integral approach of experimental and theoretical methods that provides detailed insights into the adsorption of an oxygen-tolerant [NiFe] hydrogenase on a biocompatible gold electrode. Using atomic force microscopy, ellipsometry, surface-enhanced IR spectroscopy, and protein film voltammetry, we explore enzyme coverage, integrity, and activity, thereby probing both structure and catalytic H₂ conversion of the enzyme. Electrocatalytic efficiencies can be correlated with the mode of protein adsorption on the electrode as estimated theoretically by molecular dynamics simulations. Our results reveal that pre-activation at low potentials results in increased current densities, which can be rationalized in terms of a potential-induced re-orientation of the immobilized enzyme.

International audience; The controlled incorporation of single metal nanoparticles within the pores of mesostructured conducting metal oxide ultrathin films is demonstrated, taking advantage of the controlled metal precursor loading capacities of PS-b-P4VP inverse micellar templates. The presented one-pot approach denoted as Evaporation-Induced Hydrophobic Nanoreactor Templating (EIHNT) unusually involves the nanostructuration of the metal oxide via the hydrophobic shell of the micellar template, while the concomitant nanostructuration of the metal is achieved via its confinement in the hydrophilic micellar core. This approach is applied to tin-rich ITO and gold, to yield unique mesoporous tin-rich ITO ultrathin film electrodes remarkably loaded with one size-controlled gold nanoparticle per pore. Interestingly, the resulting tin-rich ITO-supported gold nanoparticles exhibit improved catalytic activity and durability in electrocatalytic CO oxidation compared to similarly sized gold nanoparticles supported on conventional ITO coatings.