Electrocatalytic CO2 reduction: role of the cross-talk at nano-carbon interfaces

The electrocatalytic CO2 reduction reaction (CO2RR) is an interfacial process, involving a minimum of three phases at the contact point of gaseous CO2 with the electrodic surface and the liquid electrolyte. As a consequence, surface chemistry at composite interfaces plays a central role for CO2RR selectivity and catalysis. Each interface defines a functional boundary, where active sites are exposed to a unique environment, with respect to distal sites in the bulk of organic and inorganic domains. While the individual role of each component-type is hardly predictable "a-solo", the interface ensemble works via a strategic interplay of individual effects, including: (i) enhanced electrical conductivity, (ii) high surface area and exposure of the interfacial catalytic sites, (iii) favorable diffusion and feeding of reactants, (iv) complementary interactions for the "on/off" stabilization of cascade intermediates, (v) a secondary sphere assistance to lower the activation energy of bottleneck steps, (vi) a reinforced robustness and long-term operation stability. Selected CO2RR case studies are compared and contrasted to highlight how the organic domains of carbon nanostructures merge with metal and metal-oxide active sites to separate tasks but also to turn them into a cooperative asset of mutual interactions, thus going beyond the classic "Divide et Impera" rule

Water-Assisted Concerted Proton-Electron Transfer at Co(II)-Aquo Sites in Polyoxotungstates With Photogenerated RuIII(bpy)33+ Oxidant

The cobalt substituted polyoxotungstate [Co6(H2O)2(α-B-PW9O34)2(PW6O26)]17− (Co6) displays fast electron transfer (ET) kinetics to photogenerated RuIII(bpy)33+, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II)−OH2 and Co6(II)−OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)−OH moiety (Co6(III)−OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa, the Co6(II)−OH→RuIII(bpy)33+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at p

Mixing enhancement induced by viscoelastic micromotors in microfluidic platforms

Fine manipulation of fluid flows at the microscale has a tremendous impact on mass transport phenomena of chemical and biological processes inside microfluidic platforms. Fluid mixing in the laminar flow regime at low Reynolds number is poorly effective due to the inherently slow diffusive mechanism. As a strategy to enhance mixing and prompt mass transport, here, we focus on polyelectrolyte multilayer capsules (PMCs), embodying a catalytic polyoxometalate, as microobjects to create elastic turbulence and as micromotors to generate chaotic flows by fuel-fed propulsions. The effects of the elastic turbolence and of the artificial propulsion on some basic flow parameters, such as pressure and volumetric flow rate, are studied by a microfluidic set-up including pressure and flow sensors. Numerical-handling and physical models of the experimental data are presented and discussed to explain the measured dependence of the pressure drop on the flow rate in presence of the PMCs. As a practical outcome of the study, a strong decrease of the mixing time in a serpentine microreactor is demonstrated. Unlike our previous reports dealing with capillarity flow studies, the present paper relies on hydrodynamic pumping experiments, that allow us to both develop a theoretical model for the understanding of the involved phenomena and demonstrate a successful microfluidic mixing application. All of this is relevant in the perspective of developing microobject-based methods to overcome microscale processes purely dominated by diffusion with potential improvements of mass trasport in microfluidic platforms. \ua9 2019 Elsevier B.V

Pd@TiO2/carbon nanohorn electrocatalysts: reversible CO2 hydrogenation to formic acid

Direct conversion of carbon dioxide to formic acid at thermodynamic equilibrium is an advantage of enzymatic catalysis, hardly replicated by synthetic analogs, but of high priority for carbon-neutral energy schemes. The bio-mimetic potential of totally inorganic Pd@TiO2 nanoparticles is envisioned herein in combination with Single Walled Carbon NanoHorns (SWCNHs). The high surface nano-carbon entanglement templates a wide distribution of \u201chard-soft\u201d bimetallic sites where the small Pd nanoparticles (1.5 nm) are shielded within the TiO2 phase (Pd@TiO2), while being electrically wired to the electrode by the nanocarbon support. This hybrid electrocatalyst activates CO2 reduction to formic acid at near zero overpotential in the aqueous phase (onset potential at E < 120.05 V vs. RHE, pH = 7.4), while being able to evolve hydrogen via sequential formic acid dehydrogenation. The net result hints at a unique CO2 \u201ccircular catalysis\u201d where formic acid versus H2 selectivity is addressable by flow-reactor technology

Catalytic oxygen production mediated by smart capsules to modulate elastic turbulence under a laminar flow regime

none11Liquid flow in microchannels is completely laminar and uniaxial, with a very low Reynolds number regime and long mixing lengths. To increase fluid mixing and solubility of reactants, as well as to reduce reaction time, complex three-dimensional networks inducing chaotic advection have to be designed. Alternatively, turbulence in the liquid can be generated by active mixing methods (magnetic, acoustic waves, etc.) or adding small quantities of elastic materials to the working liquid. Here, polyelectrolyte multilayer capsules embodying a catalytic polyoxometalate complex have been suspended in an aqueous solution and used to create elastic turbulence and to propel fluids inside microchannels as an alternative to viscoelastic polymers. The overall effect is enhanced and controlled by feeding the polyoxometalate-modified capsules with hydrogen peroxide, H2O2, thus triggering an on-demand propulsion due to oxygen evolution resulting from H2O2 decomposition. The quantification of the process is done by analysing some structural parameters of motion such as speed, pressure, viscosity, and Reynolds and Weissenberg numbers, directly obtained from the capillary dynamics of the aqueous mixtures with different concentrations of H2O2. The increases in fluid speed as well as the capsule-induced turbulence effects are proportional to the H2O2 added and therefore dependent on the kinetics of H2O2 dismutation.Zizzari A.; Bianco M.; Miglietta R.; del Mercato L. L.; Carraro M.; Soraru A.; Bonchio M.; Gigli G.; Rinaldi R.; Viola I.; Arima, V.Zizzari, A.; Bianco, M.; Miglietta, R.; del Mercato, L. L.; Carraro, M.; Soraru, A.; Bonchio, M.; Gigli, Giuseppe; Rinaldi, Rosaria; Viola, I.; Arima, V

Light driven water oxidation by a single site cobalt salophen catalyst

A salophen cobalt(II) complex enables water oxidation at neutral pH in photoactivated sacrificial cycles under visible light, thus confirming the high appeal of earth abundant single site catalysis for artificial photosynthesis

Catalytic processing in ruthenium-based polyoxometalate coacervate protocells

The development of programmable microscale materials with cell-like functions, dynamics and collective behaviour is an important milestone in systems chemistry, soft matter bioengineering and synthetic protobiology. Here, polymer/nucleotide coacervate micro-droplets are reconfigured into membrane-bounded polyoxometalate coacervate vesicles (PCVs) in the presence of a bio-inspired Ru-based polyoxometalate catalyst to produce synzyme protocells (Ru4PCVs) with catalase-like activity. We exploit the synthetic protocells for the implementation of multi-compartmentalized cell-like models capable of collective synzyme-mediated buoyancy, parallel catalytic processing in individual horseradish peroxidase-containing Ru4PCVs, and chemical signalling in distributed or encapsulated multi-catalytic protocell communities. Our results highlight a new type of catalytic micro-compartment with multi-functional activity and provide a step towards the development of protocell reaction networks. \ua9 2020, The Author(s)

Naphthochromenones: Organic Bimodal Photocatalysts Engaging in Both Oxidative and Reductive Quenching Processes

Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale.They absorb across theUV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited-state redox potentials, PC*/PCC (up to 1.65 V) and PCC+/PC* (up to 1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis

Naphthochromenones: Organic Bimodal Photocatalysts Engaging in Both Oxidative and Reductive Quenching Processes

Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale.They absorb across theUV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited-state redox potentials, PC*/PCC (up to 1.65 V) and PCC+/PC* (up to 1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis

Spin qubits with electrically gated polyoxometalate molecules

Spin qubits offer one of the most promising routes to the implementation of quantum computers. Very recent results in semiconductor quantum dots show that electrically-controlled gating schemes are particularly well-suited for the realization of a universal set of quantum logical gates. Scalability to a larger number of qubits, however, remains an issue for such semiconductor quantum dots. In contrast, a chemical bottom-up approach allows one to produce identical units in which localized spins represent the qubits. Molecular magnetism has produced a wide range of systems with tailored properties, but molecules permitting electrical gating have been lacking. Here we propose to use the polyoxometalate [PMo12O40(VO)2]q-, where two localized spins-1/2 can be coupled through the electrons of the central core. Via electrical manipulation of the molecular redox potential, the charge of the core can be changed. With this setup, two-qubit gates and qubit readout can be implemented.Comment: 9 pages, 6 figures, to appear in Nature Nanotechnolog