The photocatalytic production of hydrogen using biopolymer-immobilized titanium dioxide (TiO) is an innovative and sustainable approach to renewable energy generation. TiO, a well-known photocatalyst, benefits from immobilization on biopolymers due to its environmental friendliness, abundance, and biodegradability. In another way, to boost the efficiency of TiO, its surface properties can be modified by incorporating co-catalysts like platinum (Pt) to improve charge separation.
View Article and Find Full Text PDFReducing the iridium demand in Proton Exchange Membrane Water Electrolyzers (PEM WE) is a critical priority for the green hydrogen industry. This study reports the discovery of a TiO-supported Ir@IrO(OH) core-shell nanoparticle catalyst with reduced Ir content, which exhibits superior catalytic performance for the electrochemical oxygen evolution reaction (OER) compared to a commercial reference. The TiO-supported Ir@IrO(OH) core-shell nanoparticle configuration significantly enhances the OER Ir mass activity from 8 to approximately 150 A g at 1.
View Article and Find Full Text PDFBipolar membranes in electrochemical CO conversion cells enable different reaction environments in the CO-reduction and O-evolution compartments. Under ideal conditions, water-splitting in the bipolar membrane allows for platinum-group-metal-free anode materials and high CO utilizations. In practice, however, even minor unwanted ion crossover limits stability to short time periods.
View Article and Find Full Text PDFThe synthesis of bimetallic and trimetallic platinum-based octahedral catalysts for the cathode of proton exchange membrane fuel cells (PEMFCs) is a particularly active area aimed at meeting technological requirements in terms of durability and cost. The electrocatalytic activity and stability of these shaped catalysts were tested at relatively high potentials (@0.9 V vs RHE) and at lower current densities using the rotating disk electrode, which is less suitable for assessing their behavior under the operating conditions of PEMFCs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Functional polymers play an important role in various biomedical applications. From many choices, poly(2-isopropenyl-2-oxazoline) (PIPOx) represents a promising reactive polymer with great potential in various biomedical applications. PIPOx, with pendant reactive 2-oxazoline groups, can be readily prepared in a controllable manner via several controlled/living polymerization methods, such as living anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation transfer (RAFT) or rare earth metal-mediated group transfer polymerization.
View Article and Find Full Text PDFIn the present work, the temperature-dependent phase behavior of a CE based microemulsion is studied in different meso-macroporous glasses, as a function of their pore diameter. The phase behavior in these pores is investigated by small-angle X-ray scattering (SAXS). The crucial parameter we discuss based on the SAXS results is the domain size of the bicontinuous phase.
View Article and Find Full Text PDFNonconductive porous polymer substrates, such as PTFE, have been pivotal in the fabrication of stable and high-performing gas diffusion electrodes (GDEs) for the reduction of CO/CO in small scale electrolyzers; however, the scale-up of polymer-based GDEs without performance penalties to technologically more relevant electrode sizes has remained elusive. This work reports on a new current collector concept that enables the scale-up of PTFE-based GDEs from 5 to 100 cm and beyond. The present approach builds on a multifunctional current collector concept that enables multipoint front-contacting of thin catalyst coatings, which mitigates performance losses even for high resistivity cathodes.
View Article and Find Full Text PDFACS Energy Lett
April 2024
Hydrogen peroxide (HO) is a widely used green oxidant. Until now, research has focused on the development of efficient catalysts for the two-electron oxygen reduction reaction (2e ORR). However, electrolyte effects on the 2e ORR have remained little understood.
View Article and Find Full Text PDFThe electrochemical reductive valorization of CO, referred to as the CO2RR, is an emerging approach for the conversion of CO-containing feeds into valuable carbonaceous fuels and chemicals, with potential contributions to carbon capture and use (CCU) for reducing greenhouse gas emissions. Copper surfaces and graphene-embedded, N-coordinated single metal atom (MNC) catalysts exhibit distinctive reactivity, attracting attention as efficient electrocatalysts for CO2RR. This review offers a comparative analysis of CO2RR on copper surfaces and MNC catalysts, highlighting their unique characteristics in terms of CO activation, C/C product formation, and the competing hydrogen evolution pathway.
View Article and Find Full Text PDFDue to their unique rheological and mechanical properties, bottlebrush polymers are inimitable components of biological and synthetic systems such as cartilage and ultrasoft elastomers. However, while their rheological properties can be precisely controlled through their macromolecular structures, the current chemical spectrum available is limited to a handful of synthetic polymers with aliphatic carbon backbones. Herein we design and synthesize a series of inorganic bottlebrush polymers based on a unique combination of polydimethylsiloxane (PDMS) and polyphosphazene (PPz) chemistry.
View Article and Find Full Text PDFExploring an active and cost-effective electrocatalyst alternative to carbon-supported platinum nanoparticles for alkaline hydrogen evolution reaction (HER) have remained elusive to date. Here, we report a catalyst based on platinum single atoms (SAs) doped into the hetero-interfaced Ru/RuO support (referred to as Pt-Ru/RuO), which features a low HER overpotential, an excellent stability and a distinctly enhanced cost-based activity compared to commercial Pt/C and Ru/C in 1 M KOH. Advanced physico-chemical characterizations disclose that the sluggish water dissociation is accelerated by RuO while Pt SAs and the metallic Ru facilitate the subsequent H* combination.
View Article and Find Full Text PDFThe amount of C in steel, which is critical in determining its properties, is strongly influenced by steel production technology. We propose a novel method of quantifying the bulk C content in steel non-destructively using muons. This revolutionary method may be used not only in the quality control of steel in production, but also in analyzing precious steel archaeological artifacts.
View Article and Find Full Text PDFMuonic helium atom hyperfine structure (HFS) measurements are a sensitive tool to test the three-body atomic system and bound-state quantum electrodynamics theory, and determine fundamental constants of the negative muon magnetic moment and mass. The world's most intense pulsed negative muon beam at the Muon Science Facility of the Japan Proton Accelerator Research Complex allows improvement of previous measurements and testing further CPT invariance by comparing the magnetic moments and masses of positive and negative muons (second-generation leptons). We report new ground-state HFS measurements of muonic helium-4 atoms at a near-zero magnetic field, performed for the first time using a small admixture of CH_{4} as an electron donor to form neutral muonic helium atoms efficiently.
View Article and Find Full Text PDFMononuclear Fe ions ligated by nitrogen (FeN) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure-reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN active centers.
View Article and Find Full Text PDFElectrochemical conversion of organic compounds holds promise for advancing sustainable synthesis and catalysis. This study explored electrochemical carbonyl hydrogenation on single-site M-N-C (Metal Nitrogen-doped Carbon) catalysts using formaldehyde, acetaldehyde, and acetone as model reactants. We strive to correlate and understand the selectivity dependence on the nature of the metal centers.
View Article and Find Full Text PDFNi-based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value-added chemicals. The identification and subsequent engineering of their catalytically active sites are essential to facilitate these anodic reactions. Herein, the proportional relationship between catalysts' deprotonation propensity and Faradic efficiency of 5-hydroxymethylfurfural (5-HMF)-to-2,5 furandicarboxylic acid (FDCA, FE ) is revealed by thorough density functional theory (DFT) simulations and atomic-scale characterizations, including in situ synchrotron diffraction and spectroscopy methods.
View Article and Find Full Text PDFCoupled tandem electrolyzer concepts have been predicted to offer kinetic benefits to sluggish catalytic reactions thanks to their flexibility of reaction environments in each cell. Here we design, assemble, test, and analyze the first complete low-temperature, neutral-pH, cathode precious metal-free tandem CO electrolyzer cell chain. The tandem system couples an Ag-free CO-to-CO/CO electrolyzer (cell-1) to a CO/CO-to-C product electrolyzer (cell-2).
View Article and Find Full Text PDFThe electrochemical conversion of 5-Hydroxymethylfurfural, especially its reduction, is an attractive green production pathway for carbonaceous e-chemicals. We demonstrate the reduction of 5-Hydroxymethylfurfural to 5-Methylfurfurylalcohol under strongly alkaline reaction environments over oxide-derived Cu bimetallic electrocatalysts. We investigate whether and how the surface catalysis of the MO phases tune the catalytic selectivity of oxide-derived Cu with respect to the 2-electron hydrogenation to 2.
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