Unravelling the Role of Free Radicals in Photocatalysis.

Free radicals are increasingly recognized as active intermediate reactive species that can participate in various redox processes, significantly influencing the mechanistic pathways of reactions. Numerous researchers have investigated the generation of one or more distinct photogenerated radicals, proposing various hypotheses to explain the reaction mechanisms. Notably, recent research has demonstrated the emergence of photogenerated radicals in innovative processes, including organic chemical reactions and the photocatalytic dissolution of precious metals. To harness the potential of these free radicals more effectively, it is imperative to consolidate and analyze the processes and action modes of these photogenerated radicals. This conceptual paper delves into the latest advancements in understanding the mechanics of photogenerated radicals.

Internal Electric Field Facilitates Facet-Dependent Photocatalytic Cl- Utilization on BiOCl in High-Salinity Wastewater for Ammonium Removal.

High Cl- concentration in saline wastewater (e.g., landfill leachate) limits wastewater purification. Catalytic Cl- conversion into reactive chlorine species (RCS) arises as a sustainable strategy, making the salinity profitable for efficient wastewater treatment. Herein, aiming to reveal the structure-property relationship in Cl- utilization, bismuth oxychloride (BiOCl) photocatalysts with coexposed {001} and {110} facets are synthesized. With an increasing {001} ratio, the RCS production efficiency increases from 75.64 to 96.89 µg L-1 min-1. Mechanism investigation demonstrates the fast release of lattice Cl- as an RCS and the compensation of ambient Cl-. Correlation analysis between the internal electric field (IEF, parallel to [001]) and normalized efficiency on {110} (kRCS/S{110}, perpendicular to [001]) displays a coefficient of 0.86, validating that the promoted carrier dynamics eventually affects Cl- conversion on the open layered structure. The BiOCl photocatalyst is well behaved in ammonium (NH4+-N) degradation ranging from 20 to 800 mg N L-1 with different chlorinity (3-12 g L-1 NaCl). The sustainable Cl- conversion into RCS also realizes 85.4% of NH4+-N removal in the treatment of realistic landfill leachate (662 mg of N L-1 NH4+-N). The structure-property relationship provides insights into the design of efficient catalysts for environment remediation using ambient Cl-.

Aqueous Electroreduction of Nitric Oxide to Ammonia at Low Concentration via Vacancy Engineered FeOCl.

Electroreduction of nitric oxide (NO) to NH3 (NORR) has gained extensive attention for the sake of low carbon emission and air pollutant treatment. Unfortunately, NORR is greatly hindered by its sluggish kinetics, especially under low concentrations of NO. Herein, we developed a chlorine (Cl) vacancy strategy to overcome this limitation over FeOCl nanosheets (FeOCl-VCl ). Density functional theory (DFT) calculations revealed that the Cl vacancy resulted in defective Fe with sharp d-states characteristics in FeOCl-VCl to enhance the absorption and activation of NO. In situ X-ray absorption near-edge structure (XANES) and attenuated total reflection-infrared spectroscopy (ATR-IR) verified the lower average oxidation state of defective Fe to enhance the electron transfer for NO adsorption/activation and facilitate the generation of key NHO and NHx intermediates. As a result, the FeOCl-VCl exhibited superior NORR activities with the NH3 Faradaic efficiency up to 91.1 % while maintaining a high NH3 yield rate of 455.4 µg cm-2 h-1 under 1.0 vol % NO concentration, competitive with those of previously reported literatures under higher NO concentration. Further, the assembled Zn-NO battery utilizing FeOCl-VCl as cathode delivered a record peak power density of 6.2 mW cm-2 , offering a new route for simultaneous NO removal, NH3 production, and energy supply.

Noble-Metal-Metalloid Alloy Architectures: Mesoporous Amorphous Iridium-Tellurium Alloy for Electrochemical N2 Reduction.

Amorphous noble metals with high surface areas have attracted significant interest as heterogeneous catalysts due to the numerous dangling bonds and abundant unsaturated surface atoms created by the amorphous phase. However, synthesizing amorphous noble metals with high surface areas remains a significant challenge due to strong isotropic metallic bonds. This paper describes the first example of a mesoporous amorphous noble metal alloy [iridium-tellurium (IrTe)] obtained using a micelle-directed synthesis method. The resulting mesoporous amorphous IrTe electrocatalyst exhibits excellent performance in the electrochemical N2 reduction reaction. The ammonia yield rate is 34.6 µg mg-1 h-1 with a Faradaic efficiency of 11.2% at -0.15 V versus reversible hydrogen electrode in 0.1 M HCl solution, outperforming comparable crystalline and Ir metal counterparts. The interconnected porous scaffold and amorphous nature of the alloy create a complementary effect that simultaneously enhances N2 absorption and suppresses the hydrogen evolution reaction. According to theoretical simulations, incorporating Te in the IrTe alloy effectively strengthens the adsorption of N2 and lowers the Gibbs free energy for the rate-limiting step of the electrocatalytic N2 reduction reaction. Mesoporous chemistry enables a new route to achieve high-performance amorphous metalloid alloys with properties that facilitate the selective electrocatalytic reduction of N2.

Fe2O3/TiO2/reduced graphene oxide-driven recycled visible-photocatalytic Fenton reactions to mineralize organic pollutants in a wide pH range.

Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe2O3/TiO2/reduced graphene oxide (FTG) nanocomposite synthesized by a facile solvothermal method. The TiO2 in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe3+-Fe2+ recycle. Meanwhile, the Fe2O3 rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectron-hole recombination. The high distribution of TiO2 and Fe2O3 on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.

Photocatalytic Free Radical-Controlled Synthesis of High-Performance Single-Atom Catalysts.

Single-atom catalysts (SACs) have emerged as crucial players in catalysis research, prompting extensive investigation and application. The precise control of metal atom nucleation and growth has garnered significant attention. In this study, we present a straightforward approach for preparing SACs utilizing a photocatalytic radical control strategy. Notably, we demonstrate for the first time that radicals generated during the photochemical process effectively hinder the aggregation of individual atoms. By leveraging the cooperative anchoring of nitrogen atoms and crystal lattice oxygen on the support, we successfully stabilize the single atom. Our Pd1 /TiO2 catalysts exhibit remarkable catalytic activity and stability in the Suzuki-Miyaura cross-coupling reaction, which was 43 times higher than Pd/C. Furthermore, we successfully depose Pd atoms onto various substrates, including TiO2 , CeO2 , and WO3 . The photocatalytic radical control strategy can be extended to other single-atom catalysts, such as Ir, Pt, Rh, and Ru, underscoring its broad applicability.

Tailoring the Asymmetric Structure of NH2 -UiO-66 Metal-Organic Frameworks for Light-promoted Selective and Efficient Gold Extraction and Separation.

Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metal-organic framework (MOF) material (NH2 -UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g g-1 under light irradiation. The selectivity of NH2 -UiO-66 for gold ions is up to 98.8 % in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH2 -UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of high-purity gold particles from NH2 -UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89 %. Theoretical calculations indicate that -NH2 functions as a dual donor of electrons and protons, and the asymmetric structure of NH2 -UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.

Subsurface Engineering Induced Fermi Level De-pinning in Metal Oxide Semiconductors for Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) water splitting is a promising approach for renewable solar light conversion. However, surface Fermi level pinning (FLP), caused by surface trap states, severely restricts the PEC activities. Theoretical calculations indicate subsurface oxygen vacancy (sub-Ov ) could release the FLP and retain the active structure. A series of metal oxide semiconductors with sub-Ov were prepared through precisely regulated spin-coating and calcination. Etching X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and electron energy loss spectra (EELS) demonstrated Ov located at sub ∼2-5 nm region. Mott-Schottky and open circuit photovoltage results confirmed the surface trap states elimination and Fermi level de-pinning. Thus, superior PEC performances of 5.1, 3.4, and 2.1 mA cm-2 at 1.23 V vs. RHE were achieved on BiVO4 , Bi2 O3 , TiO2 with outstanding stability for 72 h, outperforming most reported works under the identical conditions.

Photocatalytic Dissolution of Precious Metals by TiO2 through Photogenerated Free Radicals.

Exploring the pathways for photocatalytic dissolution of precious metals (PMs) is crucial for optimizing recovery. In this work, we systematically investigated the selectivity and solvation effects observed for dissolution by focusing on photocatalysis, precious metals and solvents. By combining transient characterization, reaction kinetics, and density functional theory, we determined that the radicals generated in photocatalysis were the key active species in the entire reaction. The cyano functional group in the solvent was the driving factor for dissolution of gold, and the importance of chlorine radicals for dissolution of platinum group precious metals was further confirmed. In addition, the catalytic properties of different precious metals can promote different transformations of functional groups, leading to selective dissolution. The structures of photocatalytic precious metal leaches also precisely explains the special coordination forms of precious metals and functional group ligands.

Photoelectrochemical sensing of dopamine using gold-TiO2 nanocomposites and visible-light illumination.

A photoelectrochemical (PEC) method was developed for the determination of dopamine. It is making use of a composite prepared from gold nanoparticles and TiO2 (type P25) and placed on a fluorine-doped tin oxide (FTO) electrode. The composites are used for photoelectrical detection with improved electron transfer efficiency for photoproduction and with improved photoelectrical conversion efficiency. This is due to the excellent electrical conductivity and surface plasmon resonance absorption by gold nanoparticles, and also by the photocatalytic effect of TiO2. Dopamine binds easily to the surface of the composites and acts as an electron donor. This electrode gives a strongly enhanced photocurrent which increases linearly in the 0.1 to 100 µM dopamine concentration range and has a 23 nM detection limit (at S/N = 3). The electrode was operated over 15 cycles of light-on and light-off states every 20 s under visible-light illumination, and the sensor indicates good stability. In addition, it is selective over several possible interferents including uric acid, L-cysteine, glutathione, ascorbic acid and glucose. Graphical abstract A new gold/P25 composite-based photoelectrochemical sensing scheme for dopamine is described. Under visible light irradiation, the photocurrent response is increased with the increasing concentration of dopamine (DA).

Correction to: Photoelectrochemical sensing of dopamine using gold-TiO2 nanocomposites and visible-light illumination.

The published version of this article, unfortunately, contains error. The author found out that Chinese characters are shown in Scheme 1a.

Unveiling the Role of Defects on Oxygen Activation and Photodegradation of Organic Pollutants.

The status of defects of TiO2 are of fundamental importance in determining its physicochemical properties. Here we report a simple chemical deposition method for controllable synthesis of defective anatase TiO2 nanocrystals under various calcination atmospheres. XPS and ESR analysis reveals that both the oxygen vacancies ( VO) and the trivalent titanium (Ti3+) defects exist in TiO2 after N2 treatment (N-TiO2). Meanwhile, mainly VO defects can be obtained in TiO2 with air calcination (A-TiO2). ESR spectra for reactive oxygen species determination, clearly show that the visible light catalytic activity is mainly caused by the efficient activation of oxygen molecules to •O2- species for A-TiO2, which play an important role in hindering the accumulation of intermediates during p-chlorophenol (4-CP) photodegradation process. However, the oxygen molecules cannot be activated for N-TiO2 even with superior visible light absorption and thus the photogenerated electron are reductant, which participated in the transformation of BQ to HQ via electron shuttle mechanism. Moreover, A-TiO2 exhibits higher separation efficiency of photogenerated carriers than that of N-TiO2, showing the critical role of VO with a suitable concentration in transferring photogenerated charges.

Enhanced Photocatalytic Degradation Performance by Fluid-Induced Piezoelectric Field.

The introduction of a piezoelectric field has been proven a promising method to enhance photocatalytic activity by preventing photoelectron-hole recombination. However, the formation of a piezoelectric field requires additional mechanical force or high-frequency ultrasonic baths, which limits its potential application on industrial scale. Therefore, it is of great practical significance to design the catalyst that can harvest the discrete energy such as the fluid mechanical energy to form the electric field. Herein, PZT/TiO2 catalyst with a core-shell configuration was prepared by a simple coating method. By collecting the mechanical energy of water, an internal piezoelectric field was induced. Under 800 rpm stirring, transient photocurrent measured on PZT/TiO2 electrode is about 1.7 times higher than that of 400 rpm. Correspondingly, the photocatalytic degradation rate and mineralization efficiency of RhB, BPA, phenol, p-chlorophenol much improved, showing the promoting effect of piezoelectric field generated directly from harvesting the discrete fluid mechanical energy.

Exploring the important role of nanocrystals orientation in TiO2 superstructure on photocatalytic performances.

Efficient charge separation has been widely accepted as one of the important factors responsible for the photocatalytic water splitting, organic oxidation, and solar cell, etc. TiO2 mesocrystal is a superstructure which could largely enhance charge separation, where TiO2 nanocrystals with parallel crystallographic alignment assemble in a form of oriented aggregation. Here, the intercrystal misorientation in TiO2 superstructure was first concerned and evaluated on the influence of photocatalytic efficiency. Our results showed that the intercrystal misorientation in TiO2 superstructures had a harmful effect on the charge separation efficiency.

Plant uptake-assisted round-the-clock photocatalysis for complete purification of aquaculture wastewater using sunlight.

A novel reactor equipped with solar batteries, Bi2O3/TiO2 film photocatalyst, and celery plant was designed and used for purification of aquaculture wastewater. The Bi2O3/TiO2 film photocatalyst started photocatalytic degradation of organonitrogen compounds under irradiation of sunlight. Meanwhile, the solar batteries absorbed and converted excess sunlight into electric energy and then started UV lamps at night, leading to round-the-clock photocatalysis. Subsequently, the inorganic nitrogen species including NH4(+), NO2(-), and NO3(-) resulting from photocatalytic degradation of the organonitrogen compounds could subsequently be uptaken by the celery plant as the fertilizer to reduce the secondary pollution. It was found that, after 24 h circulation, both organonitrogen compounds and NO2(-) species were completely removed, while NH4(+) and NO3(-) contents also decreased by 30% and 50%, respectively. The reactor could be used repetitively, showing a good potential in practical application.

Au/TiO2 superstructure-based plasmonic photocatalysts exhibiting efficient charge separation and unprecedented activity.

Plasmonic photocatalysts were successfully synthesized by the modification of TiO2 mesocrystals with Au nanoparticles (NPs) by a simple impregnation method. The Au NP sensitizers show a strong photoelectrochemical response in the visible-light region (400-800 nm) due to their surface plasmon resonance (SPR). The diffuse reflectance spectroscopy measurements on a wide range of time scales (from picoseconds to minutes) demonstrate that a substantial part of electrons, injected from the Au NPs to the TiO2 mesocrystals through the SPR excitation, directionally migrate from the basal surfaces to the edges of the plate-like mesocrystals through the TiO2 nanocrystal networks and are temporally stored there for further reactions. This anisotropic electron flow significantly retarded the charge recombination of these electrons with the holes in the Au NPs, thereby improving the visible-light-photocatalytic activity (for organic-pollutant degradation) by more than an order of magnitude, as compared to that of conventional Au/TiO2 NP systems.

Exceptional piezocatalytic H2 production of nitrogen-doped TiO2@carbon nanosheets induced by engineered piezoelectricity.

Piezocatalytic hydrogen evolution is a promising strategy to generate sustainable energy. In this report, nitrogen-doped (N-doped) TiO2@ carbon nanosheets (N-TiO2@C NSs) was successfully synthesized using C3N4 as a multifunctional template. During the synthesis, the two-dimensional (2D) architecture of C3N4 nanosheets directed the synthesis of TiO2 nanosheets. In addition, nitrogens of C3N4 were doped into the TiO2 lattice. Simultaneously, C3N4 was transformed into N-doped carbon nanosheets. N doping broke the crystal symmetry of TiO2, which endowed TiO2 with promising piezoelectric properties. The N-doped carbon nanosheets derived from C3N4 improved charge carrier separation efficiency and served as a flexible support to inhibit structural damage under sonication. Therefore, the N-TiO2@C NSs exhibited highly efficient activity for piezocatalytic H2 production (6.4 mmol·g-1·h-1) in the presence of methanol, much higher than those of the previously reported piezocatalysts. Our method is hoped to provide a new strategy for designing highly efficient piezocatalysts.

Solar-assisted selective separation and recovery of precious group metals from deactivated air purification catalysts.

The mitigation of environmental and energy crises could be advanced by reclaiming platinum group precious metals (PGMs) from decommissioned air purification catalysts. However, the complexity of catalyst composition and the high chemical inertness of PGMs significantly impede this process. Consequently, recovering PGMs from used industrial catalysts is crucial and challenging. This study delves into an environmentally friendly approach to selectively recover PGMs from commercial air purifiers using photocatalytic redox technology. Our investigation focuses on devising a comprehensive strategy for treating three-way catalysts employed in automotive exhaust treatment. By meticulously pretreating and modifying reaction conditions, we achieved noteworthy results, completely dissolving and separating rhodium (Rh), palladium (Pd), and platinum (Pt) within a 12-h time frame. Importantly, the solubility selectivity persists despite the remarkably similar physicochemical properties of Rh, Pd, and Pt. To bolster the environmental sustainability of our method, we harness sunlight as the energy source to activate the photocatalysts, facilitating the complete dissolution of precious metals under natural light irradiation. This eco-friendly recovery approach demonstrated on commercial air purifiers, exhibits promise for broader application to a diverse range of deactivated air purification catalysts, potentially enabling implementation on a large scale.

Homogeneous Carbon Dot-Anchored Fe(III) Catalysts with Self-Regulated Proton Transfer for Recyclable Fenton Chemistry.

Fenton chemistry has been widely studied in a broad range from geochemistry, chemical oxidation to tumor chemodynamic therapy. It was well established that Fe3+/H2O2 resulted in a sluggish initial rate or even inactivity. Herein, we report the homogeneous carbon dot-anchored Fe(III) catalysts (CD-COOFeIII) wherein CD-COOFeIII active center activates H2O2 to produce hydroxyl radicals (•OH) reaching 105 times larger than that of the Fe3+/H2O2 system. The key is the •OH flux produced from the O-O bond reductive cleavage boosting by the high electron-transfer rate constants of CD defects and its self-regulated proton-transfer behavior probed by operando ATR-FTIR spectroscopy in D2O and kinetic isotope effects, respectively. Organic molecules interact with CD-COOFeIII via hydrogen bonds, promoting the electron-transfer rate constants during the redox reaction of CD defects. The antibiotics removal efficiency in the CD-COOFeIII/H2O2 system is at least 51 times large than the Fe3+/H2O2 system under equivalent conditions. Our findings provide a new pathway for traditional Fenton chemistry.

2D MXenes polar catalysts for multi-renewable energy harvesting applications.

The synchronous harvesting and conversion of multiple renewable energy sources for chemical fuel production and environmental remediation in a single system is a holy grail in sustainable energy technologies. However, it is challenging to develop advanced energy harvesters that satisfy different working mechanisms. Here, we theoretically and experimentally disclose the use of MXene materials as versatile catalysts for multi-energy utilization. Ti3C2TX MXene shows remarkable catalytic performance for organic pollutant decomposition and H2 production. It outperforms most reported catalysts under the stimulation of light, thermal, and mechanical energy. Moreover, the synergistic effects of piezo-thermal and piezo-photothermal catalysis further improve the performance when using Ti3C2TX. A mechanistic study reveals that hydroxyl and superoxide radicals are produced on the Ti3C2TX under diverse energy stimulation. Furthermore, similar multi-functionality is realized in Ti2CTX, V2CTX, and Nb2CTX MXene materials. This work is anticipated to open a new avenue for multisource renewable energy harvesting using MXene materials.