The wide-scale implementation of solar and other renewable sources of electricity requires improved means for energy storage. An intriguing strategy in this regard is the reduction of CO2 to CO, which generates an energy rich commodity chemical that can be coupled to liquid fuel production. In this work, we report an inexpensive Bismuth Carbon Monoxide Evolving Catalyst (Bi-CMEC) that can be formed upon cathodic polarization of an inert glassy carbon electrode in acidic solutions containing Bi3+ ions. This catalyst can be used in conjunction with ionic liquids to effect the electrocatalytic conversion of CO2 to CO with appreciable current density at overpotentials below 0.2 V. Bi-CMEC is selective for production of CO, operating with a Faradaic efficiency of approximately 95%. When taken together these correspond to a high energy efficiency for CO production, on par with that which has historically only been observed using expensive silver and gold cathodes.

The selective reduction of oxygen to water requires four electrons and four protons. The design of catalysts that promote oxygen reduction therefore requires the management of both electron and proton inventories. Pacman and Hangman porphyrins provide a cleft for oxygen binding, a redox shuttle for oxygen reduction, and functionality for tuning the acid-base properties of bound oxygen and its intermediates. With proper control of the proton-coupled electron transfer events, O-O bond breaking of oxygen, and more generally oxygenated substrates, may be achieved with high efficiencies. The rule set developed for oxygen reduction may be applied to a variety of other small molecule activation reactions of consequence to energy conversion.

The development of inexpensive electrocatalysts that can promote the reduction of CO2 to CO with high selectivity, efficiency, and large current densities is an important step on the path to renewable production of liquid carbon-based fuels. While precious metals such as gold and silver have historically been the most active cathode materials for CO2 reduction, the price of these materials precludes their use on the scale required for fuel production. Bismuth, by comparison, is an affordable and environmentally benign metal that shows promise for CO2 conversion applications. In this work, we show that a bismuth–carbon monoxide evolving catalyst (Bi-CMEC) can be formed under either aqueous or nonaqueous conditions using versatile electrodeposition methods. In situ formation of this thin-film catalyst on an inexpensive carbon electrode using an organic soluble Bi3+ precursor streamlines preparation of this material and generates a robust catalyst for CO2 reduction. In the presence of appropriate imidazolium based ionic liquid promoters, the Bi-CMEC platform can selectively catalyze conversion of CO2 to CO without the need for a costly supporting electrolyte. This inexpensive system can catalyze evolution of CO with current densities as high as jCO = 25–30 mA/cm2 and attendant energy efficiencies of ΦCO ≈ 80% for the cathodic half reaction. These metrics highlight the efficiency of Bi-CMEC, since only noble metals have been previously shown to promote this fuel forming half reaction with such high energy efficiency. Moreover, the rate of CO production by Bi-CMEC ranges from approximately 0.1–0.5 mmol·cm−2·h−1 at an applied overpotential of η ≈ 250 mV for a cathode with surface area equal to 1.0 cm2. This CO evolution activity is much higher than that afforded by other non-noble metal cathode materials and distinguishes Bi-CMEC as a superior and inexpensive platform for electrochemical conversion of CO2 to fuel.

Nitric oxide (NO) mediates both physiological and pathological processes. 1, 2 In addition to cardiovascular signaling, NO has been invoked to play a neurochemical role in learning and memory, and it is a powerful necrotic agent wielded by macrophages of the immune system. Whereas considerable effort has been invested to develop metal-based3 -5 and other6 , 7 probes for detecting nitric oxide, there has been significantly less progress in the synthesis of platforms capable of detecting other reactive nitrogen species (RNS). 8 Of the nitrogen oxides relevant to biology, nitroxyl (HNO), the one electron reduced, protonated analog of nitric oxide,9 is among the least thoroughly investigated.10 Interest in nitroxyl has grown with the accumulation of evidence that HNO, which has a pK a of 11.4 and exists primarily in the protonated form under physiological conditions, 9 displays important biological roles with potential pharmacological applications distinct from those of nitric oxide. 11-13 For example, HNO reacts directly with thiols, 14 is resistant to scavenging by superoxide, 15 and can activate voltage-dependent K + channels in mammalian vascular systems.16 , 17 Moreover, biochemical studies suggest that HNO can be formed directly from nitric oxide synthase under appropriate conditions10 ,18 and that NO and HNO may be able to interconvert in the presence of superoxide dismutase (SOD). 19 Despite accumulating evidence of the biological importance of HNO, studies have been hampered by the lack of a biologically compatible probe for the molecule. Only recently have chemical systems capable of discerning HNO from NO been reported, but the constructs are not suitable for work with biological samples.20 , 21Properties required for selective nitroxyl detection using fluorescence methods under physiologically relevant conditions include selectivity over other reactive nitrogen species (RNS) and downstream NO oxidation products, compatibility with living biological samples, water solubility, and membrane permeability. Additionally, incorporation of a signaling moiety with relatively long-wavelength absorption and emission properties is needed to avoid unintended cellular damage by high-energy radiation and to minimize innate biological autofluorescence. BOT1 (Scheme 1) juxtaposes a BODIPY reporter site, which has optical properties that are well suited for cellular imaging experiments, 22 with a tripodal dipyridylamine appended receptor via a triazole bridge. The tripodal metal-binding site of BOT1 comprises a tertiary nitrogen bearing two 2-pyridylmethyl substituents. The third arm of the tripod is afforded by the triazole formed upon coupling of an alkyl azide with a terminal alkyne. 23 Accordingly, the triazole arm completes the tripodal coordination environment engendered by the N-(triazolylmethyl)-N,N-dipicolyl framework while simultaneously providing a rigid spacer between the BODIPY reporter and chelating ligand. This design serves The photophysical properties of BOT1 were assessed under simulated physiological co...

Energy conversion cycles are aimed at driving unfavorable, small-molecule activation reactions with a photon harnessed directly by a transition-metal catalyst or indirectly by a transition-metal catalyst at the surface of a photovoltaic cell. The construction of such cycles confronts daunting challenges because they rely on chemical transformations not understood at the most basic levels. These transformations include multielectron transfer, proton-coupled electron transfer, and bond-breaking and -making reactions of energy-poor substrates. We have begun to explore these poorly understood areas of molecular science with transition-metal complexes that promote hydrogen production and oxygen bond-breaking and -making chemistry of consequence to water splitting.

The development of affordable electrocatalysts that can drive the reduction of CO2 to CO with high selectivity, efficiency, and large current densities is a critical step on the path to production of liquid carbon-based fuels. In this work, we show that inexpensive triflate salts of Sn(2+), Pb(2+), Bi(3+), and Sb(3+) can be used as precursors for the electrodeposition of CO2 reduction cathode materials from MeCN solutions, providing a general and facile electrodeposition strategy, which streamlines catalyst synthesis. The ability of these four platforms to drive the formation of CO from CO2 in the presence of [BMIM]OTf was probed. The electrochemically prepared Sn and Bi catalysts proved to be highly active, selective, and robust platforms for CO evolution, with partial current densities of jCO = 5-8 mA/cm(2) at applied overpotentials of η < 250 mV. By contrast, the electrodeposited Pb and Sb catalysts do not promote rapid CO generation with the same level of selectivity. The Pb material is only ∼10% as active as the Sn and Bi systems at an applied potential of E = -1.95 V and is rapidly passivated during catalysis. The Sb-comprised cathode material shows no activity for conversion of CO2 to CO under analogous conditions. When taken together, this work demonstrates that 1,3-dialkylimidazoliums can promote CO production, but only when used in combination with an appropriately chosen electrocatalyst material. More broadly, these results suggest that the interactions between CO2, the imidazolium promoter, and the cathode surface are all critical to the observed catalysis.

We report an efficient electrochemical conversion of CO2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim]­[OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi3+ species) formed during the synthesis and purification process hinders the CO2 reduction, leading to a 20% drop in Faradaic efficiency for CO evolution (FECO). Bi particle size showed a significant effect on FECO when the surface of Bi was air-oxidized, but this effect of size on FECO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO2 to CO (96.1% FECO), and a mass activity for CO evolution (MACO) of 15.6 mA mg–1, which is three-fold higher than the conventional Bi-ED, at −2.0 V (vs Ag/AgCl). This work elucidates the importance of the surface activation for an efficient electrochemical CO2 conversion on metal NPs and paves the way for understanding the CO2 electrochemical reduction mechanism in nonaqueous media.

Rapid bioorthogonal reactivity can be induced by controllable, catalytic stimuli using air as the oxidant. Methylene blue (4 μM) irradiated with red light (660 nm) catalyzes the rapid oxidation of a dihydrotetrazine to a tetrazine thereby turning on reactivity toward trans-cyclooctene dienophiles. Alternately, the aerial oxidation of dihydrotetrazines can be efficiently catalyzed by nanomolar levels of horseradish peroxidase under peroxide-free conditions. Selection of dihydrotetrazine/tetrazine pairs of sufficient kinetic stability in aerobic aqueous solutions is key to the success of these approaches. In this work, polymer fibers carrying latent dihydrotetrazines were catalytically activated and covalently modified by trans-cyclooctene conjugates of small molecules, peptides and proteins. In addition to visualization with fluorophores, fibers conjugated to a cell adhesive peptide exhibited a dramatically increased ability to mediate contact guidance of cells.