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A comprehensive and reliable view on the influence of UV light and heat on optical properties of ZnO shall be outlined mainly based on research conducted by scientists from Warsaw Pact countries throughout the twentieth century. The problems of language barrier and loss of knowledge are being addressed. An insight into processes of photodesorption and photoadsorption of oxygen and other gas phase molecules leading to changes in charge carrier states is outlined. While desorption of surface adsorbates leads to increased number of conduction electrons and thus increased absorbance of infrared light, adsorption of electronegative gas phase molecules leads to quenching in fluorescence.

Using a series of ordered mesoporous TiO2 (om-TiO2) with and without Ce or Cu doping, the effects of structure, metal doping and residual template species in the structure are systematically evaluated in terms of products formed during a CO2 photoreduction process. It is found that the ordered mesoporous structure contributes significantly in the hydrogen evolution reaction from the splitting of gaseous water. No cocatalyst was needed to achieve high hydrogen yields. While carbon-containing products are also observed, the presence of remainders of the organic template used in the synthesis process does not allow an unambiguous identification of the source of products. Small amounts of metal doping do not majorly influence the hydrogen evolution, thus the mesoporous structure can eventually be identified as the main cause for the improved performance.

Due to significant advances in instrumentation, many previously specialized techniques have become “routine” in user facilities. However, detailed knowledge held by experts has often not been relayed to general users, so they often rely on entry-level information, basic principles, and comparison with literature results for data analysis. As a result, major errors in the data analysis of multiple surface and material analysis techniques, including in x-ray photoelectron spectroscopy (XPS), have been appearing in the scientific literature. Representative examples of serious errors in XPS data analysis are shown in this work. We suggest that surface and material analysis, and perhaps even science in general, are in a state of “pre-crisis.” We use two (logistic) models from population biology to suggest that bad analyses self-correct if they remain below a critical number. However, beyond a threshold, the literature can become useless because of the perpetuation of faulty analyses and concomitant loss of its self-correcting ability. XPS is used by scientists in many communities because of the power of the technique and high-quality instrumentation that is commercially available. Those who make new surfaces and materials face unique challenges because of the large number of surface and material analytical techniques that are often needed to characterize their materials. Graduate students and post-docs are often provided with only minimal instruction on using surface and material characterization methods. High fees for instruments may affect both the quality and the quantity of the data people collect. The Prisoner's Dilemma is a model from game theory that describes situations with reward structures that encourage uncooperative behavior and lead to suboptimal outcomes. However, the outcomes of Prisoner's Dilemma are not inevitable—their consequences change if their reward structures change. The current system does not appear to incentivize detailed learning of surface and material characterization techniques and careful material characterization. Prisoner's dilemmas appear to lead to other undesirable consequences in science. The concerns raised in this work suggest that many manuscripts are incompletely reviewed at present. The different stakeholders in this problem, including authors, research advisers, subject matter experts, reviewers, scientists who notice examples of faulty data analysis, editors, journals and publishers, funding agencies, scientific societies, leaders at universities and research centers, and instrument vendors, can improve the current situation. This work provides specific recommendations for each of these stakeholders. For example, we believe that authors are primarily responsible for the correctness of their work, not reviewers or editors; we question the wisdom of listing the names of the editor and reviewers on a paper; we are grateful for the significant contributions that have been made by subject matter experts to produce standards and tutorial information; the high cost of instrument time at some institutions may limit student access and result in suboptimal analyses; staff scientists often need to be better recognized for their intellectual contributions to studies; publishers may wish to allow selective reviewing of specific sections of papers related to material characterization; the reviewing at some open access journals may be inadequate; while it had its shortcomings, the pre-open access model of publishing incentivized the production and publication of high-quality work; audits of the products (scientific papers) of funding agencies may be necessary; collaboration needs to be encouraged to a greater extent at some institutions; and instrument vendors should not suggest to potential customers that surface characterization, e.g., by XPS, is trivial or simple.

s This work describes the synthesis of porous hierarchical microspheres composed of amorphous SiO2 and crystalline β-Bi2O3 (BSO) via a simple solvothermal process and subsequent calcination. Complementary physicochemical methods were applied to study the function of amorphous SiO2, as well as the phase composition and morphology evolution of as-synthesized samples as a function of calcination temperature. The presence of amorphous SiO2 contributed to form hierarchically structured β-Bi2O3 with enhanced thermostability. Moreover, the degradation of tetracycline hydrochloride (TC) under visible light irradiation was employed as a model reaction to evaluate the photocatalytic activity of as prepared materials. In consequence, both phase composition and morphology were found to be significant parameters for adjusting the photocatalytic performance of the synthesized samples. The fastest TC degradation at a low dosage of catalyst (0.2 g L-1) was observed for the sample annealed at 400℃ which contains a highly crystalline β-Bi2O3 phase. The synergistic effect of the porous structure, excellent light absorption, and higher charge carrier separation and transfer efficiency is believed to be the reason for the optimal photocatalytic activity. This study offers a new method toward the fabrication of hierarchical porous structured β-Bi2O3 with enhanced thermostability for various applications.

In this study nitrogen-doped carbon quantum dots/graphitic carbon nitride nanosheet (CNQD) composites with different contents of nitrogen-doped carbon quantum dots (NCQDs; 2, 4, 6, and 8 wt%) were synthesized. The morphological, physicochemical, and photoelectrochemical properties were investigated using complementary methods such as scanning electron microscopy (SEM), powder X-ray diffraction (pXRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), UV/Vis spectroscopy in diffuse reflectance (DRS), photoluminescence (PL), nitrogen physisorption (BET), photocurrent response, and electrochemical impedance spectroscopy (EIS). The photocatalytic activity of the synthesized materials was assessed during diclofenac (DCF) degradation in an aqueous solution under visible light irradiation. As a result, improved photocatalytic efficiency in DCF degradation was observed for all the CNQD composites compared with bulk graphitic carbon nitride (bCN) and nanosheet g-C3N4 (CNS). The fastest DCF degradation was observed for the 6 wt% NCQD on the surface of CNS (CNQD-6), which removed 62% of DCF in 3 h, with an associated k value of 5.41 × 10−3 min−1. The performance test results confirmed the contribution of NCQDs to enhancing photocatalytic activity, leading to an improvement factor of 1.24 over bCN. The morphology of the CNS and the synergistic interaction between NCQDs and CNS were essential elements for enhancing photocatalytic activity. The photoelectrochemical data and photoluminescence analyses showed the efficient migration of photoexcited electrons from NCQDs to the CNS. The reduced charge recombination rates in CNQD photocatalysts might be due to the synergistic interaction between NCQDs and CNS and the unique up-conversion photoluminescence properties of NCQDs. Further investigations revealed that the photogenerated superoxide radicals (•O2−) predominated in the degradation of DCF, and this photocatalyst had good reusability and toxicity reduction abilities. This work provides insight into the effects of NCQDs on the CNS surface to enhance its potential to remove emerging organic pollutants from water and wastewater.

Evidence is provided that in a gas-solid photocatalytic reaction the removal of photogenerated holes from a titania (TiO2 ) photocatalyst is always detrimental for photocatalytic CO2 reduction. The coupling of the reaction to a sacrificial oxidation reaction hinders or entirely prohibits the formation of CH4 as a reduction product. This agrees with earlier work in which the detrimental effect of oxygen-evolving cocatalysts was demonstrated. Photocatalytic alcohol oxidation or even overall water splitting proceeds in these reaction systems, but carbon-containing products from CO2 reduction are no longer observed. H2 addition is also detrimental, either because it scavenges holes or because it is not an efficient proton donor on TiO2 . The results are discussed in light of previously suggested reaction mechanisms for photocatalytic CO2 reduction. The formation of CH4 from CO2 is likely not a linear sequence of reduction steps but includes oxidative elementary steps. Furthermore, new hypotheses on the origin of the required protons are suggested.

Regulating the transfer pathway of charge carriers in heterostructure photocatalysts is of great importance for selective CO

A comprehensive and reliable view on the influence of UV light and heat on optical properties of ZnO shall be outlined mainly based on research conducted by scientists from Warsaw Pact countries throughout the 20th century. The problems of language barrier and loss of knowledge are being addressed. An insight into processes of photodesorption and photoadsorption of oxygen and other gas phase molecules leading to changes in charge carrier states is outlined. While desorption of surface adsorbates leads to increased number of conduction electrons and thus increased absorbance of infrared light, adsorption of electronegative gas phase molecules leads to quenching in fluorescence.

Supported vanadium oxide species are tested for their capability to perform photocatalytic methyl orange degradation in the aqueous phase. Excitation is performed with a frequency-tripled (λ=270 nm) or frequency-doubled (λ=405 nm) Ti:sapphire laser in a newly designed 15 ml photoreactor. Photocatalytic activity in dye degradation is only observed at 270 nm excitation, indicating that larger vanadium oxide structures (V₂O₅ nanoparticles, decavanadates) are either not present in sufficient quantities, or not active in the reaction. Reference experiments exclude pure photodegradation of the dye. It is found that a major part of the supported vanadium oxide species becomes detached from the silica support, and a very small fraction detaches from alumina. Considerations of the aqueous phase chemistry of dissolved vanadate ions allow to identify the formed dissolved species to be predominantly H₂VO₄− ions. These doubly protonated monovanadates are the main active species in the photocatalytic reaction, together with small anchored species on alumina.

Driven by the necessity of a sustainable living of future generations, semiconductor-based photocatalysis gained increasing attention in various research fields like green energy conversion or pollutant degradation. Neat semiconductors are often found to be rather inactive due to insufficient valence/conduction band potentials, short carrier lifetime and mobility, demanding noble metal cocatalysts and/or heterojunctions with other semiconductors. A famous example for an efficient neat photocatalyst is often found in Zinc Sulfide due to its beneficial photophysical properties concerning charge carrier formation, high activity in water reduction without precious cocatalysts, and earth-abundance. Unfortunately, the high susceptibility of ZnS and its paramount role to photocorrosion is often neglected or only addressed in passing. To circumvent the low photostability of ZnS, the addition of sacrificial agents before photocatalytic testing is state-of-the-art but appears to stand without question in most publications. Using sacrificial agents is however far from reasonable as the former are constantly consumed in substantial amounts rendering the commonly claimed arguments of sustainability and economic feasibility of ZnS a potential misconception worth critically reviewing. Hence, with this review, we take a step back to objectively but also critically review the facts regarding photocorrosion and applicability of Zinc Sulfide photocatalysis.

Evidence is provided that in a gas-solid photocatalytic reaction the removal of photogenerated holes from a titania (TiO

This work describes the synthesis of porous hierarchical microspheres composed of amorphous SiO

Photocatalytic carbon dioxide reduction utilizing metal complexes based on the earth-abundant transition metals iron and copper was transferred from organic solvents into ionic liquids with high selectivity and moderate turn-over numbers. Different classes of ionic liquids were evaluated to determinate the CO/H2 selectivity of the process. High-purity conditions were utilized to validate that CO was a result of CO2 reduction and not resulting from other carbon sources. In addition, a novel copper-based photosensitizer was synthesized and its photo- and electrochemical properties were investigated.

Ordered mesoporous titanium dioxide with different Fe, Co and Ni content (0.5 and 5 mol%) has been synthesized by co-precipitation using the evaporation–induced self-assembly (EISA) method combined with the liquid crystal templating (LCT) pathway. The structural characteristics of the prepared materials have been studied by several analytical techniques. Small-angle X-ray scattering was used to follow the effect of single synthesis steps on mesoporous ordering. The materials obtained after final calcination were characterized by scanning transmission electron microscopy, X-ray diffraction, electron paramagnetic resonance, UV/visible diffuse reflectance spectroscopy, and nitrogen adsorption-desorption. At low metal content (0.5 mol%) the presence of the doping metal has only a minor impact on the mesoporous ordering of the titania structure obtained after calcination. At higher doping metal content (5 mol%) the structural characteristics depend on the particular metal. The synthesized materials have been tested in photocatalytic degradation of phenol under UV irradiation. The influence of structural parameters such as BET surface area, pore volume, and degree of ordering on phenol degradation were insignificant. Photocatalytic activity depends mainly on the particular metal and its amount. Titania doped with 0.5 mol% Fe or Co showed improved phenol degradation compared to the pristine titania.

In this paper the applicability of selected silica-supported early transition metal oxides in photocatalysis is discussed. The catalytic properties of highly dispersed transition metal oxides often differ strongly from their corresponding bulk material. The structural and photophysical properties can often be linked to those changes.

Perovskites such as SrTiO3 are interesting for photocatalytic applications due to their structure-related and electronic properties. These properties are influenced by the presence of SrCO3 which is often formed simultaneously during the hydrothermal synthesis of SrTiO3. In this study, SrTiO3-SrCO3 composites with different contents of SrCO3 (5–24 wt%) were synthesized. Their morphological, structural, and optical properties were investigated using complementary methods such as scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen sorption, and diffuse reflectance spectroscopy (DRS). Their photocatalytic activity was assessed during the degradation of diclofenac (DCFNa) in aqueous solution and CO2 photoreduction under Xe lamp irradiation. Improved photocatalytic efficiency in DCFNa degradation was observed for all the studied composites in comparison with SrTiO3, and the highest mineralization efficiency was obtained for the sample with 21 wt% SrCO3 content. The presence of SrCO3 led to an increased concentration of active species, such as •OH radicals. Otherwise, its presence inhibits CH4 and C2H6 production during CO2 photoreduction compared with pure SrTiO3.

Engineering of defects in semiconductors provides an effective protocol for improving photocatalytic N2 conversion efficiency. This review focuses on the state-of-the-art progress in defect engineering of photocatalysts for the N2 reduction toward ammonia. The basic principles and mechanisms of thermal catalyzed and photon-induced N2 reduction are first concisely recapped, including relevant properties of the N2 molecule, reaction pathways, and NH3 quantification methods. Subsequently, defect classification, synthesis strategies, and identification techniques are compendiously summarized. Advances of in situ characterization techniques for monitoring defect state during the N2 reduction process are also described. Especially, various surface defect strategies and their critical roles in improving the N2 photoreduction performance are highlighted, including surface vacancies (i.e., anionic vacancies and cationic vacancies), heteroatom doping (i.e., metal element doping and nonmetal element doping), and atomically defined surface sites. Finally, future opportunities and challenges as well as perspectives on further development of defect-engineered photocatalysts for the nitrogen reduction to ammonia are presented. It is expected that this review can provide a profound guidance for more specialized design of defect-engineered catalysts with high activity and stability for nitrogen photochemical fixation.

Although the photocatalytic reduction of CO2 to CH4 by using H2O as the oxidant presupposes the formation of O2, it is often not included in the product analysis of most of the studies dealing with photocatalytic CO2 reduction or it is reported to be not formed at all. The present study aims to clarify the absence of O2 in the photocatalytic gas phase CO2 reduction on TiO2. By modifying P25-TiO2 with IrOx co-catalysts it was possible to observe photocatalytic water splitting, i.e. the formation of gaseous O2 and H2 in almost stoichiometric amounts, without the use of sacrificial agents, while bare P25-TiO2 showed no activity in H2 and O2 formation under similar reaction conditions. Investigating the effect of improved H2O oxidation properties on the photocatalytic CO2 reduction revealed that the CH4 formation on P25 from CO2 was completely inhibited as long as the H2O splitting reaction proceeded. Furthermore, we found that a certain amount of O2 is consumed under conditions of photocatalytic water oxidation. A quantification showed it to be in the same order of magnitude as the oxygen which is missing as a byproduct from photocatalytic CO2 conversion. A detailed interpretation of the results in the context of the general understanding of the photocatalytic CO2 reduction with H2O on TiO2 allows the hypothesis that P25-TiO2 undergoes a stoichiometric reaction, meaning that the CH2 formation is not based on a true catalytic cycle and runs only as long as TiO2 can consume oxygen.

By a combination of electron paramagnetic resonance spectroscopy, finite-temperature ab initio simulations, and electronic structure analyses, the activation of molecular dioxygen at the interface of gold nanoparticles and titania in Au/TiO2 catalysts is explained at the atomic scale by tracing processes down to the molecular orbital picture. Direct evidence is provided that excess electrons in TiO2, for example created by photoexcitation of the semiconductor, migrate to the gold particles and from there to oxygen molecules adsorbed at gold/titania perimeter sites. Superoxide species are formed more efficiently in this way than on the bare TiO2 surface. This catalytic effect of the gold nanoparticles is attributed to a weakening of the internal O-O bond, leading to a preferential splitting of the molecule at shorter bond lengths together with a 70% decrease of the dissociation free energy barrier compared to the non-catalyzed case on bare TiO2. The findings are an important step forward in the clarification of the role of gold in (photo)catalytic processes.

Au/TiO2 catalysts in different geometrical arrangements were designed to explore the role of morphology and structural properties for the photocatalytic reduction of CO2 with H2 O in the gas-phase. The most active sample was a Au@TiO2 core-shell catalyst with additional Au nanoparticles (NPs) deposited on the outer surface of the TiO2 shell. CH4 and CO are the primary carbon-containing products. Large amounts of H2 are additionally formed by photocatalytic H2 O splitting. Shell thickness plays a critical role. The highest yields were observed with the thickest layer of TiO2 , stressing the importance of the semiconductor for the reaction. Commercial TiO2 with and without Au NPs was less active in the production of CH4 and CO. The enhanced activation of CO2 on the core-shell system is concluded to result from electronic interaction between the gold core, the titania shell, and the Au NPs on the outer surface. The improved exposure of Au-TiO2 interface contributes to the beneficial effect.

Photocatalytic CO2 conversion to hydrocarbons (sometimes referred to as 'artificial photosynthesis'), which mimics natural photosynthesis with purely inorganic photocatalysts, has the potential to simultaneously combat the energy crisis and the greenhouse effect. In more than half of all reported studies to date, TiO2 -based materials are used as the photocatalyst. Yet, the reaction conditions and reactor designs employed in previous studies cover a vast range, hindering mutual comparisons of observed activities and selectivity. In this work, a systematic literature study is attempted, including a selection of only such research publications which report experimental conditions of high purity and a proof of the carbon source (blank experiments, 13 CO2 isotope labelling or stoichiometric O2 identification) for CO2 photoreduction. General trends were then detected and discussed, aiming to guide future research to more efficient photocatalytic systems.

The transformation of CO2 into fuels and chemicals by photocatalysis is a promising strategy to provide a long-term solution to mitigating global warming and energy-supply problems. Achievements in photocatalysis during the last decade have sparked increased interest in using sunlight to reduce CO2 . Traditional semiconductors used in photocatalysis (e.g. TiO2 ) are not suitable for use in natural sunlight and their performance is not sufficient even under UV irradiation. Some two-dimensional (2D) materials have recently been designed for the catalytic reduction of CO2 . These materials still require significant modification, which is a challenge when designing a photocatalytic process. An overarching aim of this Review is to summarize the literature on the photocatalytic conversion of CO2 by various 2D materials in the liquid phase, with special attention given to the development of novel 2D photocatalyst materials to provide a basis for improved materials.

In this issue of Chem Catalysis, Huang, Li, and co-workers report an innovative strategy for suppressing unwanted hydrogen oxidation in preferential oxidation of carbon monoxide (CO-PROX). Through plasmonic excitation of gold, lead oxide is selectively photodeposited at the interface, poisoning highly active but nonselective sites.

Ordered titanium dioxide nanotube arrays fabricated via electrochemical route are considered as a promising material for photocatalytic applications. Due to their amorphous character, a subsequent crystallization step is usually required. In this work, well-aligned nanotube arrays were annealed under flowing gas streams of different compositions (air/steam, air, N2/steam, N2, and O2/steam) in a temperature range from 140 to 543 °C. Under continuous gas flow, the morphology of the crystallized titanium dioxide is strongly affected by the gas atmosphere. When using a dry gas for annealing, the tube structure was almost destroyed after 1 h treatment at 473 °C. In contrast, when annealing the titania nanotube array in a water vapor/gas stream, the tube morphology can be maintained up to 543 °C and 10 h annealing time. Moreover, nanotube arrays crystallized in a flowing gas atmosphere containing water vapor showed a significantly higher photocatalytic activity for phenol degradation under UV irradiation than nanotube arrays crystallized in a dry gas stream. Reasons for this behavior might be the preservation of the tubular structure as well as a lower concentration or density of structural defects in presence of water vapor which leads to an enhanced generation of reactive oxygen species when the arrays are exposed to UV-light.

Zinc oxide (ZnO) with a high potentiality for tunable morphology is gaining immense research interests for targeted environmental remediation of emerging micropollutants in source waters. Various three-dimensional (3D) flower-like nanostructures of ZnO were synthesized by following a facile and low-temperature hydrothermal synthesis approach, using Zn(CH3COO)2∙2H2O as the starting precursor reagent, in the presence of different bases at varying concentrations as the structure-directing reagents. BET studies indicated that the ZnO-flowers 1 were more superior than ZnO-flowers 2 and 3, as it possessed the highest specific surface area (10.83 m2/g), pore volume (0.054 cm3/g) and pore size (23.52 nm). Subsequently, the photoactivities of ZnO-flowers on the degradation of emerging salicylic acid micropollutant under UV-A illumination were examined. Batch studies suggested that the ZnO-flowers were photoactive and photocatalysed optimally under neutral pH condition that are aligned with the cost-effective and practical implementation for water/wastewater treatment. ZnO-flowers 1 demonstrated the highest photoactivity according to its reaction rate constant, where the kinetics data was well-fitted using the pseudo-first order Langmuir-Hinshelwood rate equation. This finding was well correlated to the BET studies, where the high photoactivity in ZnO-flowers 1 could be ascribed to its exceptional surface morphology that maximises the surface contact area with salicylic acid during photodegradation. Finally, the radicals trapping experiments were carried out in order to validate the role of primary photogenerated holes (h+) and various secondary reactive oxygen species (ROS) in the photodegradation of salicylic acid using ZnO-flowers photocatalysts. It was confirmed that the active species of photogenerated h+, •OH, and •O2− were responsible for the photodegradation process. The plausible mechanistic pathways for the reaction between scavenging reagents and the reactive transitory species to form by-products and intermediates were also proposed.

As part of an ongoing effort to understand the deactivation and improve the stability of metal oxide-supported Au catalysts in the low-temperature CO oxidation reaction while maintaining their high activity, we have investigated the influence of a mesoporous silica SBA-15 substrate on the activity and stability of Au/TiO2 catalysts, which consist of a SBA-15 support surface modified by a monolayer of TiOx with Au nanoparticles on top. The extent of the TiOx surface modification was systematically increased, while the Au loading and the Au particle sizes were largely kept constant. Employing kinetic measurements at three different temperatures (30 °C, 80 °C, 180 °C) and a number of ex situ methods as well as in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for catalyst characterization, we found that the activity of these catalysts increases significantly with the Ti concentration and with reaction temperature. The tendency for deactivation remains essentially unchanged. Detailed in situ DRIFTS measurements reveal that the Au nanoparticles are largely formed on the TiOx surface-modified areas of the SBA-15 support and that the tendency for surface carbonate formation is very low. The observed deactivation may at least partly be related to the accumulation of molecularly adsorbed H2O species, in particular at low temperatures (30 °C). These are likely to be formed from surface hydroxyl groups, they may affect the reaction either by blocking of active sites or by blocking the adsorption of reactants on the substrate. Other effects, such as reaction induced changes in the titania layer, must however, play a role as well, both at 80 °C and in particular at 180 °C, where accumulation of adsorbed species is negligible. The mechanistic ideas are supported by reactivation tests subsequent to calcination at 400 °C, which were found to fully restore the initial activity.

Transition metal oxide overlayers are an important class of heterogeneous catalysts (sometimes referred to as monolayer catalysts), both for model studies and numerous industrial processes. To determine the molecular structures in such amorphous thin layers requires application of characterization methods that can perform in the absence of long-range order and can distinguish between different molecular structures of the same metal oxide (e.g., isolated VO4, isolated VO5, isolated VO6, dimeric V2O7, oligomeric (VO3)n, etc.). Vibrational spectroscopy (IR and Raman) is the method of choice for this purpose since it can discriminate among multiple molecular structures and can function at high temperatures and pressures in presence of reactive gas phases (oxidizing, reducing and in between). Thus, IR and Raman spectroscopy uniquely provide access to in situ and operando molecular spectroscopy studies under relevant catalytic reaction conditions. In the present review, a comprehensive overview of the various possibilities to structurally and chemically characterize oxide overlayers with vibrational spectroscopy is presented and the progress achieved so far in this field is summarized. The surface molecular structures of supported transition metal oxide layers on oxide supports are described in detail, focusing in particular on those vibrational modes that can be used for precise molecular structural determination. The structural response of such surface oxide species to environmental conditions (ambient, dehydrated, reduced, reaction conditions) is reviewed. The approaches employed to characterize adsorption and reaction sites by the adsorption of suitable probe molecules or by performing in situ or operando studies will be discussed in detail. Additionally, the use of vibrational spectroscopy to study more complex systems will be highlighted, such as the formation of native oxide overlayers on complex oxides or even metal particles (e.g., during strong metal–support interactions).

By a combination of FT-NIR Raman spectroscopy, infrared spectroscopy of CO adsorption under ultrahigh vacuum conditions (UHV-IR) and Raman spectroscopy in the line scanning mode the formation of a reduced titania phase in a commercial Au/TiO2 catalyst and in freshly prepared Au/anatase catalysts was detected. The reduced phase, formed at the Au-TiO2 interface, can serve as nucleation point for the formation of stoichiometric rutile. TinO2n−1 Magneli phases, structurally resembling the rutile phase, might be involved in this process. The formation of the reduced phase and the rutilization process is clearly linked to the presence of gold nanoparticles and it does not proceed under similar conditions with the pure titania sample. Phase transformations might be both thermally or light induced, however, the colloidal deposition synthesis of the Au/TiO2 catalysts is clearly ruled out as cause for the formation of the reduced phase.

Crystalline TiO2 (P25) and isolated titanate species in a ZSM-5 structure (TS-1) were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic CO2 reduction under high purity conditions. The noble metal modification was performed by photodeposition. Light absorbance properties of the catalysts are examined with UV–Vis spectroscopy before and after the activity test. In the gas-phase photocatalytic CO2 reduction, it was observed that the catalysts with Ag nanostructures are more active than those with Au nanostructures. It is thus found that the energetic difference between the band gap energy of the semiconductor and the position of the plasmon is influencing the photocatalytic activity. Potentially, plasmon excitation due to visible light absorption results in plasmon resonance energy, which affects the excitation of the semiconductor positively. Therefore, an overlap between band gap energy of the semiconductor and metal plasmon is needed.

In this study we assess the general applicability of the widely used P25-TiO2 in gas-phase photocatalytic CO2 reduction based on experimentally determined reactivity descriptors from classical heterogeneous catalysis (productivity) and photochemistry (apparent quantum yield/AQY). A comparison of the results with reports on the use of P25 for thermodynamically more feasible reactions and our own previous studies on P25-TiO2 as photocatalyst imply that the catalytic functionality of this material, rather than its properties as photoabsorber, limits its applicability in the heterogeneous photocatalytic CO2 reduction in the gas phase. The AQY of IrOx/TiO2 in overall water splitting in a similar high-purity gas-solid process was four times as high, but still far from commercial viability.

In this study we assess the general applicability of the widely used P25-TiO

Although the photocatalytic reduction of CO2 to CH4 by using H2O as the oxidant presupposes the formation of O2, it is often not included in the product analysis of most of the studies dealing with photocatalytic CO2 reduction or it is reported to be not formed at all. The present study aims to clarify the absence of O2 in the photocatalytic gas phase CO2 reduction on TiO2. By modifying P25-TiO2 with IrOx co-catalysts it was possible to observe photocatalytic water splitting, i.e. the formation of gaseous O2 and H2 in almost stoichiometric amounts, without the use of sacrificial agents, while bare P25-TiO2 showed no activity in H2 and O2 formation under similar reaction conditions. Investigating the effect of improved H2O oxidation properties on the photocatalytic CO2 reduction revealed that the CH4 formation on P25 from CO2 was completely inhibited as long as the H2O splitting reaction proceeded. Furthermore, we found that a certain amount of O2 is consumed under conditions of photocatalytic water oxidation. A quantification showed it to be in the same order of magnitude as the oxygen which is missing as a byproduct from photocatalytic CO2 conversion. A detailed interpretation of the results in the context of the general understanding of the photocatalytic CO2 reduction with H2O on TiO2 allows the hypothesis that P25-TiO2 undergoes a stoichiometric reaction, meaning that the CH4 formation is not based on a true catalytic cycle and runs only as long as TiO2 can consume oxygen.

Commercial TiO2 (anatase) was successfully modified with Ag nanoparticles at different nominal loadings (1%&ndash, 4%) using a liquid impregnation method. The prepared materials retained the anatase structure and contained a mixture of Ag0 and AgI species. Samples exhibited extended light absorption to the visible region. The effect of Ag loading on TiO2 is studied for the photocatalytic reduction of CO2 to CH4 in a gas&ndash, solid process under high-purity conditions. It is remarkable that the reference TiO2 used in this work is entirely inactive in this reaction, but it allows for studying the effect of Ag on the photocatalytic process in more detail. Only in the case of 2% Ag/TiO2 was the formation of CH4 from CO2 observed. Using different light sources, an influence of the localized surface plasmon resonance (LSPR) effect of Ag is verified. A sample in which all Ag has been reduced to the metallic state was less active than the respective sample containing both Ag0 and Ag+, indicating that a mixed oxidation state is beneficial for photocatalytic performance. These results contribute to a better understanding of the effect of metal modification of TiO2 in photocatalytic CO2 reduction.

Zinc sulfide has unique and easily modifiable photophysical properties and is a promising candidate for photocatalysis and optoelectronic devices. However, ZnS suffers from corrosive decomposition during excitation processes like UV irradiation, which drastically limits its field of potential applications. For the first time, complete photostabilization of individual ZnS particles by a dense, durable, and only 3-nm-thick Al₂O₃ layer, produced by rotary atomic layer deposition (ALD) is reported. In contrast to bare ZnS, the coated particles do not suffer from photocorrosive degradation even under long-term or high power UV irradiation. The presence of a protection layer covering the entire ZnS surface is additionally confirmed by microscopic and spectroscopic investigations of particle cross-sections. Further, complete inhibition of the reaction between Ag⁺ ions added as the analyte and the ZnS surface is observed. Durability tests of the as-prepared Al₂O₃ layer upon prolonged exposure to water reveal a significant decrease in the protection capability of the layer, which is ascribed to the hydrolysis of the amorphous Al₂O₃. A calcination step at 1000 °C after the ALD treatment, which leads to crystallization of the amorphous Al₂O₃ layer, successfully suppresses this hydrolysis and produces an insulating, dense, and inert protection layer.