Atomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media.

Electrochemical hydrogen peroxide (H2O2) production (EHPP) via a two-electron oxygen reduction reaction (2e- ORR) provides a promising alternative to replace the energy-intensive anthraquinone process. M-N-C electrocatalysts, which consist of atomically dispersed transition metals and nitrogen-doped carbon, have demonstrated considerable EHPP efficiency. However, their full potential, particularly regarding the correlation between structural configurations and performances in neutral media, remains underexplored. Herein, a series of ultralow metal-loading M-N-C electrocatalysts are synthesized and investigated for the EHPP process in the neutral electrolyte. CoNCB material with the asymmetric Co-C/N/O configuration exhibits the highest EHPP activity and selectivity among various as-prepared M-N-C electrocatalyst, with an outstanding mass activity (6.1 × 105 A gCo-1 at 0.5 V vs. RHE), and a high practical H2O2 production rate (4.72 mol gcatalyst-1 h-1 cm-2). Compared with the popularly recognized square-planar symmetric Co-N4 configuration, the superiority of asymmetric Co-C/N/O configurations is elucidated by X-ray absorption fine structure spectroscopy analysis and computational studies.

Operando XAFS investigation on the effect of ash deposition on three-way catalyst used in gasoline particulate filters and the effect of the manufacturing process on the catalytic activity.

Platinum group metals such as palladium and rhodium based catalysts are currently being implemented in gasoline particulate filter (GPF) autoexhaust after treatment systems. However, little is known about how the trapped particulate matter, such as the incombustible ash, interacts with the catalyst and so may affect its performance. Thisoperandostudy follows the evolution of the Pd found in two different model GPF systems: one containing ash components extracted from a GPF and another from a catalyst washcoat prior to adhesion onto the GPF. We show that the catalytic activity of the two systems vary when compared with a 0 g ash containing GPF. Compared to the 0 g ash sample the 20 g ash containing sample had a higher CO light off temperature, in addition, an oscillation profile for CO, CO2and O2was observed, which is speculated to be a combination of CO oxidation, C deposition via a Boudouard reaction and further partial oxidation of the deposited species to CO. During the ageing procedure the washcoat sample reduces NO at a lower temperature than the 0 g ash sample. However, post ageing the 0 g ash sample recovers and both samples reduce NO at 310 °C. In comparison, the 20 g ash GPF sample maintains a higher NO reduction temperature of 410 °C post ageing, implying that the combination of high temperature ageing and presence of ash has an irreversible negative effect on catalyst performance.

Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria.

Supported atomic metal sites have discrete molecular orbitals. Precise control over the energies of these sites is key to achieving novel reaction pathways with superior selectivity. Here, we achieve selective oxygen (O2) activation by utilising a framework of cerium (Ce) cations to reduce the energy of 3d orbitals of isolated copper (Cu) sites. Operando X-ray absorption spectroscopy, electron paramagnetic resonance and density-functional theory simulations are used to demonstrate that a [Cu(I)O2]3- site selectively adsorbs molecular O2, forming a rarely reported electrophilic η2-O2 species at 298 K. Assisted by neighbouring Ce(III) cations, η2-O2 is finally reduced to two O2-, that create two Cu-O-Ce oxo-bridges at 453 K. The isolated Cu(I)/(II) sites are ten times more active in CO oxidation than CuO clusters, showing a turnover frequency of 0.028 ± 0.003 s-1 at 373 K and 0.01 bar PCO. The unique electronic structure of [Cu(I)O2]3- site suggests its potential in selective oxidation.

Synergistic ultraviolet and visible light photo-activation enables intensified low-temperature methanol synthesis over copper/zinc oxide/alumina.

Although photoexcitation has been employed to unlock the low-temperature equilibrium regimes of thermal catalysis, mechanism underlining potential interplay between electron excitations and surface chemical processes remains elusive. Here, we report an associative zinc oxide band-gap excitation and copper plasmonic excitation that can cooperatively promote methanol-production at the copper-zinc oxide interfacial perimeter of copper/zinc oxide/alumina (CZA) catalyst. Conversely, selective excitation of individual components only leads to the promotion of carbon monoxide production. Accompanied by the variation in surface copper oxidation state and local electronic structure of zinc, electrons originating from the zinc oxide excitation and copper plasmonic excitation serve to activate surface adsorbates, catalysing key elementary processes (namely formate conversion and hydrogen molecule activation), thus providing one explanation for the observed photothermal activity. These observations give valuable insights into the key elementary processes occurring on the surface of the CZA catalyst under light-heat dual activation.

The influence of porosity on nanoparticle formation in hierarchical aluminophosphates.

In this work we explore the deposition of gold onto a silicoaluminophosphate, using a variety of known nanoparticle deposition techniques. By comparing the gold particles deposited on a traditional microporous aluminophosphate, with an analogous hierarchical species, containing both micropores and mesopores, we explore the influence of this dual porosity on nanoparticle deposition. We show that the presence of mesopores has limited influence on the nanoparticle properties, but allows the system to maintain porosity after nanoparticle deposition. This will aid diffusion of reagents through the system, allowing continued access to the active sites in hierarchical systems, which offers significant potential in catalytic oxidation/reduction reactions.

Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene.

The interaction of CO with an attapulgite-supported Cu(ii)Cl2 catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by using a catalyst pre-treatment where the supported Cu(ii)Cl2 sample is exposed to a diluted stream of chlorine. Subsequent CO exposure at ∼370 °C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of X-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu+ and a small amount of Cu2+. Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu+/Cu2+ catalyst is required to support CO chemisorption.