In situ Electron Paramagnetic Resonance Spectroelectrochemical Study of Graphene-based Supercapacitors: Comparison between Chemically Reduced Graphene Oxide and Nitrogen-doped Reduced Graphene Oxide

An in situ electrochemical electron paramagnetic resonance (EPR) spectroscopic study of N-doped reduced graphene oxide (N-rGO) is reported with the aim of understanding the properties of this material when employed as an electrical double-layer capacitor. N-rGO shows a capacitance of 100 F g−1 in 6 M KOH, which is twice that found for reduced graphene oxide (rGO). The temperature dependence of the rGO EPR signal revealed two different components: a narrow component, following the Curie law, was related to defects; and a broad curve with a stronger Pauli law component was attributed to the spin interaction between mobile electrons and localised π electrons trapped at a more extended aromatic structure. The N-rGO sample presented broader EPR signals, indicative of additional contributions to the resonance width. In situ EPR electrochemical spectroscopy was applied to both samples to relate changes in unpaired electron density to the enhanced capacitance. The narrow and broad components increased and diminished reversibly with potential. The potential-dependent narrow feature was related to the generated radical species from corresponding functional groups: e.g. O- and N-centred radicals. Improved capacitance seen for the N-modified basal graphene planes can be accordingly suggested to underlie the enhanced capacitance of N-rGO in basic electrolytes

Amplification of Fluctuations in Unstable Systems with Disorder

We study the early-stage kinetics of thermodynamically unstable systems with quenched disorder. We show analytically that the growth of initial fluctuations is amplified by the presence of disorder. This is confirmed by numerical simulations of morphological phase separation (MPS) in thin liquid films and spinodal decomposition (SD) in binary mixtures. We also discuss the experimental implications of our results.Comment: 15 pages, 4 figure

New Insights into the Mechanism of Visible Light Photocatalysis

ABSTRACT: In recent years, the area of developing visible-lightactive photocatalysts based on titanium dioxide has been enormously investigated due to its wide range of applications in energy and environment related fields. Various strategies have been designed to efficiently utilize the solar radiation and to enhance the efficiency of photocatalytic processes. Building on the fundamental strategies to improve the visible light activity of TiO2-based photocatalysts, this Perspective aims to give an insight into many contemporary developments in the field of visible-light-active photocatalysis. Various examples of advanced TiO2 composites have been discussed in relation to their visible light induced photoconversion efficiency, dynamics of electron− hole separation, and decomposition of organic and inorganic pollutants, which suggest the critical need for further development of these types of materials for energy conversion and environmental remediation purposes

Enhancement of the Electron Spin Resonance of Single-Walled Carbon Nanotubes by Oxygen Removal

We have observed a nearly fourfold increase in the electron spin resonance (ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to oxygen desorption. By performing temperature-dependent ESR spectroscopy both before and after thermal annealing, we found that the ESR in SWCNTs can be reversibly altered via the molecular oxygen content in the samples. Independent of the presence of adsorbed oxygen, a Curie-law (spin susceptibility $\propto 1/T$) is seen from $\sim$4 K to 300 K, indicating that the probed spins are finite-level species. For both the pre-annealed and post-annealed sample conditions, the ESR linewidth decreased as the temperature was increased, a phenomenon we identify as motional narrowing. From the temperature dependence of the linewidth, we extracted an estimate of the intertube hopping frequency; for both sample conditions, we found this hopping frequency to be $\sim$100 GHz. Since the spin hopping frequency changes only slightly when oxygen is desorbed, we conclude that only the spin susceptibility, not spin transport, is affected by the presence of physisorbed molecular oxygen in SWCNT ensembles. Surprisingly, no linewidth change is observed when the amount of oxygen in the SWCNT sample is altered, contrary to other carbonaceous systems and certain 1D conducting polymers. We hypothesize that physisorbed molecular oxygen acts as an acceptor ($p$-type), compensating the donor-like ($n$-type) defects that are responsible for the ESR signal in bulk SWCNTs.Comment: 14 pages, 7 figure

Advanced photocatalytic materials

Semiconductor photocatalysts have attracted a great amount of multidiscipline research due to their distinctive potential for solar-to-chemical-energy conversion applications, ranging from water and air purification to hydrogen and chemical fuel production. This unique diversity of photoinduced applications has spurred major research efforts on the rational design and development of photocatalytic materials with tailored structural, morphological, and optoelectronic properties in order to promote solar light harvesting and alleviate photogenerated electron-hole recombination and the concomitant low quantum efficiency. This book presents a collection of original research articles on advanced photocatalytic materials synthesized by novel fabrication approaches and/or appropriate modifications that improve their performance for target photocatalytic applications such as water (cyanobacterial toxins, antibiotics, phenols, and dyes) and air (NOx and volatile organic compounds) pollutant degradation, hydrogen evolution, and hydrogen peroxide production by photoelectrochemical cells. © 2020 by the authors

Photonic crystal-assisted visible light activated TiO2 photocatalysis

Photonic crystals have been established as unique periodic structures to promote photon capture and control over light-matter interactions. Their application in semiconductor, mainly TiO2, photocatalysis has emerged as a promising structural modification to boost light harvesting of photocatalytic materials by means of slow photons i.e. light propagation at reduced group velocity near the edges of the photonic band gap (PBG). In this review, the latest advances in the development of TiO2 photonic crystal photocatalysts are highlighted, targeting primarily on the design, fabrication, structure-activity and performance evaluation of visible light activated (VLA) TiO2 inverse opals in the degradation of water and air pollutants as well as water splitting. Up to date work demonstrating the amplification effect of PBG engineered photonic crystals on the photocatalytic and photoelectrochemical performance under UV excitation is accordingly presented. Recent developments on the combination of enhanced light trapping, mainly via slow photons, mass transport and adsorption of macro/mesoporous inverse opals with targeted compositional and electronic modifications currently pursued to promote charge separation and visible light activation, i.e. dye sensitization, non-metal and self-doping, coupling with metallic nanoparticles and plasmonic effects, heterostructuring with narrow band gap semiconductors, quantum dots and graphene as well as the use of alternative metal oxide photocatalysts beyond TiO2 are thoroughly reviewed with respect to their potential for key improvements of the photocatalytic efficiency under visible light. Pertinent challenges and future prospects in photonic crystal-assisted VLA photocatalysts are addressed aimed at advanced photon management routes that could step up photocatalytic applications. © 2018 Elsevier B.V