A Study in Red: The Overlooked Role of Azo-Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption.

The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430-450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470 nm) for H2 evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies.

On the importance of catalysis in photocatalysis: Triggering of photocatalysis at well-defined anatase TiO2 crystals through facet-specific deposition of oxygen reduction cocatalyst.

Well-defined anatase TiO2 crystals with co-exposed {101} and {001} facets represent a promising platform for fundamental studies in photocatalysis and for the development of novel photocatalytic systems exhibiting higher than usual quantum efficiencies. Herein, we present protocols enabling the photoreductive deposition of Pt nanoparticles onto anatase TiO2 micro-sized (1-3 µm) crystals prepared by hydrothermal growth in fluoride-containing solutions to be carried out either facet-selectively (on {101} facets only) or facet-non-selectively (on both {101} and {001} facets). The photocatalytic behavior of the resulting photocatalysts is studied using investigations of oxidative photodegradation of a test pollutant [4-chlorophenol (4-CP)], photocurrent measurements, and kinetic analysis of the open-circuit photopotential decay. We demonstrate that the deposition of Pt nanoparticles effectively triggers the photocatalytic degradation of 4-CP at anatase crystals that are otherwise completely inactive. The role of Pt in triggering the photocatalysis is demonstrated to consist chiefly in the catalytic enhancement of the reaction rate of oxygen reduction by the photogenerated electrons. Only the platinized {101} facets contribute to photocatalysis, whereas the {001} facets, in the literature often referred to as "highly reactive", are even after platinization completely inactive, most likely due to (1 × 4) surface reconstruction upon the heat treatment necessary to decrease the amount of surface fluorides. Based on our results, we highlight the eminent role of efficient surface catalysis for effective charge separation and provide specific design rules for further development of photocatalysts with high quantum efficiencies.

Water-Soluble Polymeric Carbon Nitride Colloidal Nanoparticles for Highly Selective Quasi-Homogeneous Photocatalysis.

Heptazine-based polymeric carbon nitrides (PCN) are promising photocatalysts for light-driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom-up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi-homogeneous conditions. The superior performance of water-soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H2 O2 production via reduction of oxygen accompanied by highly selective photooxidation of 4-methoxybenzyl alcohol and benzyl alcohol or lignocellulose-derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re-dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.

Enhancing Photocatalysis: Understanding the Mechanistic Diversity in Photocatalysts Modified with Single-Atom Catalytic Sites.

Surface modification of heterogeneous photocatalysts with single-atom catalysts (SACs) is an attractive approach for achieving enhanced photocatalytic performance. However, there is limited knowledge of the mechanism of photocatalytic enhancement in SAC-modified photocatalysts, which makes the rational design of high-performance SAC-based photocatalysts challenging. Herein, a series of photocatalysts for the aerobic degradation of pollutants based on anatase TiO2 modified with various low-cost, non-noble SACs (vanadate, Cu, and Fe ions) is reported. The most active SAC-modified photocatalysts outperform TiO2 modified with the corresponding metal oxide nanoparticles and state-of-the-art benchmark photocatalysts such as platinized TiO2 and commercial P25 powders. A combination of in situ electron paramagnetic resonance spectroscopy and theoretical calculations reveal that the best-performing photocatalysts modified with Cu(II) and vanadate SACs exhibit significant differences in the mechanism of activity enhancement, particularly with respect to the rate of oxygen reduction. The superior performance of vanadate SAC-modified TiO2 is found to be related to the shallow character of the SAC-induced intragap states, which allows for both the effective extraction of photogenerated electrons and fast catalytic turnover in the reduction of dioxygen, which translates directly into diminished recombination. These results provide essential guidelines for developing efficient SAC-based photocatalysts.

Photodriven Charge Accumulation and Carrier Dynamics in a Water-Soluble Carbon Nitride Photocatalyst.

Charge accumulation in photoactive molecules and materials holds great promise in solar energy conversion as it allows for decoupling solar-driven charging from (dark) redox reactions. In this contribution, light-driven charge accumulation was investigated for a recently reported novel water-soluble carbon nitride [K,Na-poly(heptazine imide); K,Na-PHI] photocatalyst, which exhibits excellent activity and stability in highly selective photocatalytic oxidation of alcohols and concurrent reduction of dioxygen to H2 O2 under quasi-homogeneous conditions. An excellent charge storage ability of the K,Na-PHI material was demonstrated, showing an optimal density of accumulated electrons (32.2 µmol of electrons per gram) in the presence of 10 vol % MeOH as a sacrificial electron donor. The long-lived electrons accumulated under anaerobic conditions as K,Na-PHI.- radical ions were utilized in interfacial electron transfer to O2 or methyl viologen in a subsequent dark reaction. Ultrafast time-resolved spectroscopy was employed to reveal the kinetics of charge-carrier recombination and methanol oxidation. Geminate recombination of electrons and holes within approximately 100 ps was followed by trap-assisted recombination. The presence of methanol as a sacrificial electron donor accelerated the decay of the transient absorption signal when a static sample was used. This behavior was ascribed to the faster charge recombination in the presence of the radical anions generated after hole extraction. The work suggests that photodriven electron storage in the water-soluble carbon nitride is enabled by localized trap states, and highlights the importance of the effective electron donor for creating long-lived photo-generated carbon nitride radicals.

Ultrafast anisotropic exciton dynamics in a water-soluble ionic carbon nitride photocatalyst.

Ultrafast transient absorption anisotropy spectroscopy (TAA) reveals the orientational dynamics of light-induced excitations in a water soluble poly(heptazine imide). The results provide insights into the fast charge transfer processes in the material.

Sol-Gel Processing of Water-Soluble Carbon Nitride Enables High-Performance Photoanodes*.

In spite of the enormous promise that polymeric carbon nitride (PCN) materials hold for various applications, the fabrication of high-quality, binder-free PCN films and electrodes has been a largely elusive goal to date. Here, we tackle this challenge by devising, for the first time, a water-based sol-gel approach that enables facile preparation of thin films based on poly(heptazine imide) (PHI), a polymer belonging to the PCN family. The sol-gel process capitalizes on the use of a water-soluble PHI precursor that allows formation of a non-covalent hydrogel. The hydrogel can be deposited on conductive substrates, resulting in formation of mechanically stable polymeric thin layers. The resulting photoanodes exhibit unprecedented photoelectrochemical (PEC) performance in alcohol reforming and highly selective (∼100 %) conversions with very high photocurrents (>0.25 mA cm-2 under 2 sun) down to <0 V vs. RHE. This enables even effective PEC operation under zero-bias conditions and represents the very first example of a 'soft matter'-based PEC system capable of bias-free photoreforming. The robust binder-free films derived from sol-gel processing of water-soluble PCN thus constitute a new paradigm for high-performance 'soft matter' photoelectrocatalytic systems and pave the way for further applications in which high-quality PCN films are required.

Intercalation and Deintercalation of Lithium at the Ionic Liquid-Graphite(0001) Interface.

The intercalation and deintercalation of lithium (Li) into / out of graphite(0001), which is a highly important process in Li-ion batteries, was investigated under ultrahigh vacuum conditions as a function of temperature, employing X-ray and ultraviolet photoelectron spectroscopy. Both the up-shifts of the core-level binding energy and the lowering of the work function ΔΦ reveal that heating of a monolayer of the battery-relevant ionic liquid (IL) 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]+[TFSI]-) adsorbed on lithiated graphite at 80 K to >230 K facilitates an accumulation of partially charged Liδ+ atoms at the IL-graphite(0001) interface. This is accompanied by a partial IL decomposition, which is associated with the initial stages of the chemical formation of the solid-electrolyte interphase.