Two-Dimensional Perovskite Oxynitride K2LaTa2O6N with an H+/K+ Exchangeability in Aqueous Solution Forming a Stable Photocatalyst for Visible-Light H2 Evolution

Undoped layered oxynitrides have not been considered as promising H₂-evolution photocatalysts because of the low chemical stability of oxynitrides in aqueous solution. Here, we demonstrate the synthesis of a new layered perovskite oxynitride, K₂LaTa₂O₆N, as an exceptional example of a water-tolerant photocatalyst for H₂ evolution under visible light. The material underwent in-situ H⁺/K⁺ exchange in aqueous solution while keeping its visible-light-absorption capability. Protonated K₂LaTa₂O₆N, modified with an Ir cocatalyst, exhibited excellent catalytic activity toward H₂ evolution in the presence of I⁻ as an electron donor and under visible light; the activity was six times higher than Pt/ZrO₂/TaON, one of the best-performing oxynitride photocatalysts for H₂ evolution. Overall water splitting was also achieved using the Ir-loaded, protonated K₂LaTa₂O₆N in combination with Cs-modified Pt/WO₃ as an O₂ evolution photocatalyst in the presence of an I₃⁻/I⁻ shuttle redox couple.     

Undoped Layered Perovskite Oxynitride Li2LaTa2O6N for Photocatalytic CO2 Reduction with Visible Light

Oxynitrides are promising visible‐light‐responsive photocatalysts, but their structures are almost confined with three‐dimensional (3D) structures such as perovskites. A phase‐pure Li₂LaTa₂O₆N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium‐rich oxide precursor. Li₂LaTa₂O₆N exhibited high crystallinity and visible‐light absorption up to 500 nm. As opposed to well‐known 3D oxynitride perovskites, Li₂LaTa₂O₆N supported by a binuclear Ru^II complex was capable of stably and selectively converting CO₂ into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li₂LaTa₂O₆N possesses a lower density of mid‐gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.     

A Methylthio‐Functionalized‐MOF Photocatalyst with High Performance for Visible‐Light‐Driven H2 Evolution

Recently, the emergence of photoactive metal–organic frameworks (MOFs) has given great prospects for their applications as photocatalytic materials in visible‐light‐driven hydrogen evolution. Herein, a highly photoactive visible‐light‐driven material for H₂ evolution was prepared by introducing methylthio terephthalate into a MOF lattice via solvent‐assisted ligand‐exchange method. Accordingly, a first methylthio‐functionalized porous MOF decorated with Pt co‐catalyst for efficient photocatalytic H₂ evolution was achieved, which exhibited a high quantum yield (8.90 %) at 420 nm by use sacrificial triethanolamine. This hybrid material exhibited perfect H₂ production rate as high as 3814.0 μmol g^?1 h^?1, which even is one order of magnitude higher than that of the state‐of‐the‐art Pt/MOF photocatalyst derived from aminoterephthalate.     

Ultrathin Metal–Organic Framework Nanosheets with Ultrahigh Loading of Single Pt Atoms for Efficient Visible‐Light‐Driven Photocatalytic H2 Evolution

A surfactant‐stabilized coordination strategy is used to make two‐dimensional (2D) single‐atom catalysts (SACs) with an ultrahigh Pt loading of 12.0 wt %, by assembly of pre‐formed single Pt atom coordinated porphyrin precursors into free‐standing metal–organic framework (MOF) nanosheets with an ultrathin thickness of 2.4±0.9 nm. This is the first example of 2D MOF‐based SACs. Remarkably, the 2D SACs exhibit a record‐high photocatalytic H₂ evolution rate of 11 320 μmol g^?1 h^?1 via water splitting under visible light irradiation (λ>420 nm) compared with those of reported MOF‐based photocatalysts. Moreover, the MOF nanosheets can be readily drop‐casted onto solid substrates, forming thin films while still retaining their photocatalytic activity, which is highly desirable for practical solar H₂ production.     

Synthesis of noble‐metal‐free ternary K7HNb6O19/Cd0.5Zn0.5S/g‐C3N4 tandem heterojunctions for efficient photocatalytic performance under visible light

Exploring noble‐metal‐free, highly active and durable catalysts is vital to get to grips with the energy and environmental issues. Herein, we first dexterously design and synthesize a class of ternary Nb₆/CZS/g‐CN photocatalysts for the removal of hexavalent chromium Cr (VI) and organic dye pollutant (MO) from wastewater under visible‐light irradiation. A heterojunction Nb₆–1/CZS/g‐CN loaded with 0.01 g K₇HNb₆O₁₉ showed excellent photocatalytic performance, with the MO photodegradation efficiency of 94% in 1 h and the Cr (VI) (150 mg/l) photoreduction efficiency as high as 91% in 2 hr. The main active species were deemed to be O₂^.‐. Additionally, the as‐prepared ternary heterojunction exhibits superior hydrogen evolution reaction (HER) rate. A heterojunction Nb₆–4/CZS/g‐CN loaded with 0.5 g K₇HNb₆O₁₉ exhibited the highest H₂ evolution rate as high as 1777.86 μmol h^?1 g^?1 under visible‐light illumination, which is increased to 5.7 and 2.7 times that of bare CZS and biphase heterojunction CZS/g‐CN_. These findings afford a new class of promising low‐cost photocatalyst bodying for its huge potential value in sustainable energy development and wastewater treatment.     

Visible Light Photocatalytic Activity of Pt/N‐TiO2 towards Enhanced H2 Production from Water Splitting

Present work mainly focuses on experimental investigation to improvement of hydrogen production by water photoelectrolysis. An experimental facility was designed and constructed for visible light photocatalysis. A series of N‐TiO₂ photocatalysts impregnated with platinum on the surface of N‐TiO₂ were prepared. Hydrogen production upon irradiating aqueous Pt/N‐TiO₂ suspension with visible light was investigated. The shift in excitation wavelength of TiO₂ was 380 nm improved the yield of hydrogen production by N‐TiO₂ and Pt/N‐TiO₂. We used a 400 W mercury arc lamp combined with a 400 nm cutoff filter eliminating all the wavelengths under 400 nm. Pt/N‐TiO₂ material was characterized with TPR, reflective UV/Visible spectroscopy and TEM. The best hydrogen production rate obtained for this setup for N/Ti = 10, 0.05 wt% Pt/N‐TiO₂, through water splitting was about 772 μmolh^?1g^?1.     

Efficient Visible‐Light‐Driven Z‐Scheme Overall Water Splitting Using a MgTa2O6−xNy /TaON Heterostructure Photocatalyst for H2 Evolution

An (oxy)nitride‐based heterostructure for powdered Z‐scheme overall water splitting is presented. Compared with the single MgTa₂O_6?xN_y or TaON photocatalyst, a MgTa₂O_6?xN_y /TaON heterostructure fabricated by a simple one‐pot nitridation route was demonstrated to effectively suppress the recombination of carriers by efficient spatial charge separation and decreased defect density. By employing Pt‐loaded MgTa₂O_6?xN_y /TaON as a H₂‐evolving photocatalyst, a Z‐scheme overall water splitting system with an apparent quantum efficiency (AQE) of 6.8 % at 420 nm was constructed (PtO_x‐WO₃ and IO₃^?/I^? pairs were used as an O₂‐evolving photocatalyst and a redox mediator, respectively), the activity of which is circa 7 or 360 times of that using Pt‐TaON or Pt‐MgTa₂O_6?xN_y as a H₂‐evolving photocatalyst, respectively. To the best of our knowledge, this is the highest AQE among the powdered Z‐scheme overall water splitting systems ever reported.     

Core–Shell‐Structured LaTaON2 Transformed from LaKNaTaO5 Plates for Enhanced Photocatalytic H2 Evolution

LaTaON₂ is a photocatalyst with intense visible light absorption up to 650 nm, but exhibits low H₂ evolution activity owing to uncontrolled facets and high defect densities. In this work, core–shell‐structured plate‐like LaKNaTaO₅/LaTaON₂ was synthesized by nitriding a layered perovskite‐type LaKNaTaO₅. The volatilization of K and Na species during the nitridation promoted the rapid transformation of LaKNaTaO₅ into LaTaON₂ along [010] direction with the plate‐like shape retained. This yielded high‐quality LaTaON₂ shells exposing (010) facets on the lattice‐matched LaKNaTaO₅ cores. After loading with a Rh co‐catalyst, LaKNaTaO₅/LaTaON₂ showed photocatalytic H₂ evolution activity four times greater than that obtained from conventional irregular‐shaped LaTaON₂ powders and utilized visible light up to 620 nm. This work provides a novel strategy yielding oxynitrides with well‐defined facets and low defect densities by selecting lattice‐matched oxide precursors containing volatile components.     

Multifunctional Nitrogen‐Doped Carbon Nanodots for Photoluminescence,Sensor, and Visible‐Light‐Induced H2 Production

Herein, multifunctional N‐doped carbon nanodots (NCNDs) were prepared through the one‐step hydrothermal treatment of yeast. Results show that the NCNDs can be used as a new photocatalyst to drive the water‐splitting reaction under UV light. Moreover, the NCNDs can efficiently catalyze the hydrogen evolution reaction. Under visible‐light irradiation, Eosin Y‐sensitized NCNDs exhibit excellent activity for hydrogen evolution. The hydrogen evolution rate of NCNDs (without any modification and co‐catalyst) reaches 107.1 μmol h^?1 (2142 μmol g^?1 h^?1). When Pt is loaded on the NCNDs, the hydrogen evolution rate reaches 491.2 μmol h^?1 (9824 μmol g^?1 h^?1) under visible‐light irradiation. In addition, the NCNDs show excellent fluorescent properties and can be applied as a fluorescent probe for the sensitive and selective detection of Fe³⁺.     

In‐situ Platinum Plasmon Resonance Effect Prompt Titanium Dioxide Nanocube Photocatalytic Hydrogen Evolution

Herein, Pt‐decorated TiO₂ nanocube hierarchy structure (Pt‐TNCB) was fabricated by a facile solvothermal synthesis and in‐situ photodeposition strategy. The Pt‐TNCB exhibits an excellent solar‐driven photocatalytic hydrogen evolution rate (337.84 μmol h^?1), which is about 37 times higher than that of TNCB (9.19 μmol h^?1). Interestingly, its photocatalytic property is still superior to TNCB with post modification Pt (1 wt %) (208.11 μmol h^?1). The introduction of Pt efficiently extends the photoresponse of the composite material from UV to visible light region, simultaneously boosting their solar‐driven photocatalytic performance, which attribute to the porous structure, the sub size TNCB, the SPR effect of Pt NPs and strong interaction of two components. In fact, Pt NPs can enhance collective oscillations on delocalized electrons, which is conducive to capture electrons and hinder the recombination of photogenerated electron‐hole pairs, leading to the longer lifetime of photogenerated charges. The fabrication of Pt‐TNCB photocatalyst with SPR effect may provide a promising method to improve visible‐light photocatalytic activities for traditional photocatalysts.     

Photocatalyst Materials for Water Splitting

Various photocatalyst materials developed by the group of the present author are described. Alkali and alkaline earth tantalates have arisen as a new group of photocatalyst materials for splitting of water into H₂ and O₂ under ultraviolet irradiation. They showed activities even without co-catalysts such as Pt, being different from titanate photocatalysts. When NiO co-catalysts were loaded on the tantalate photocatalysts, the photocatalytic activities were markedly increased. Among the tantalates, NiO/NaTaO₃ doped with La showed the highest activity. BiVO₄, AgNO₃, and TiO₂ co-doped with Cr and Sb photocatalysts showed high activities for O₂ evolution in the presence of a sacrificial reagent (Ag⁺) under visible light irradiation ( > 420 nm). Pt/SrTiO₃ co-doped with Cr and Sb or Ta, Pt/NaInS₂, and Pt/AgInZn₇S₉ photocatalysts showed high activities for H₂ evolution from aqueous solutions containing reducing reagents under visible light irradiation. Furthermore, Cu- or Ni-doped ZnS photocatalysts showed H₂ evolution activities even without co-catalysts such as Pt.     

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors

Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H₂ evolution due to their long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH₂‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H₂ evolution under visible light irradiation. Especially, NH₂‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H₂ evolution rate of 23.41 mmol g^?1 h^?1 (with the TOF of 402.36 h^?1), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H₂ evolution among various MOF‐ and COF‐based photocatalysts.     

Anthraquinone Redox Relay for Dye‐Sensitized Photo‐electrochemical H2O2 Production

Anthraquinone (AQ) redox mediators are introduced to metal‐free organic dye sensitized photo‐electrochemical cells (DSPECs) for the generation of H₂O₂. Instead of directly reducing O₂ to produce H₂O₂, visible‐light‐driven AQ reduction occurs in the DSPEC and the following autooxidation with O₂ allows H₂O₂ accumulation and AQ regeneration. In an aqueous electrolyte, under 1 sun conditions, a water‐soluble AQ salt is employed with the highest photocurrent of up to 0.4 mA cm^?2 and near‐quantitative faradaic efficiency for producing H₂O₂. In a non‐aqueous electrolyte, under 1 sun illumination, an organic‐soluble AQ is applied and the photocurrent reaches 1.8 mA cm^?2 with faradaic efficiency up to 95 % for H₂O₂ production. This AQ‐relay DSPEC exhibits the highest photocurrent so far in non‐aqueous electrolytes for H₂O₂ production and excellent acid stability in aqueous electrolytes, thus providing a practical and efficient strategy for visible‐light‐driven H₂O₂ production.     

Iridium and Rhodium Complexes within a Macroreticular Acidic Resin: A Heterogeneous Photocatalyst for Visible‐light Driven H2 Production without an Electron Mediator

Direct ion exchange of cyclometalated iridium(III) and tris‐2,2′‐bipyridyl rhodium(III) complexes, of which the former acts as a photosensitizer and the latter as a proton reduction catalyst, within a macroreticular acidic resin has been accomplished with the aim of developing a photocatalyst for H₂ production under visible‐light irradiation. Ir L_III‐edge and Rh K‐edge X‐ray absorption fine structure (XAFS) measurements suggest that the Ir and Rh complexes are easily accommodated in the macroreticular space without considerable structural changes. The photoluminescence emission of the exchanged Ir complex due to a triplet ligand charge‐transfer (³LC) and metal‐to‐ligand charge‐transfer (³MLCT) transition near 550 nm decreases with increasing the amount of the Rh complex, thus suggesting the occurrence of an electron transfer from Ir to Rh. The Ir‐Rh/resin catalyst behaves as a heterogeneous photocatalyst capable of both visible‐light sensitization and H₂ production in an aqueous medium in the absence of an electron mediator. The photocatalytic activitity is strongly dependent on the amount of the components and reaches a maximum at a molar ratio of 2:1 of Ir/Rh complexes. Moreover, leaching and agglomeration of the active metal complexes are not observed, and the recovered photocatalyst can be recycled without loss in catalytic activity.     

Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction

As a metal‐free nitrogen reduction reaction (NRR) photocatalyst, g‐C₃N₄ is available from a scalable synthesis at low cost. Importantly, it can be readily functionalized to enhance photocatalytic activities. However, the use of g‐C₃N₄‐based photocatalysts for the NRR has been questioned because of the elusive mechanism and the involvement of N defects. This work reports the synthesis of a g‐C₃N₄ photocatalyst modified with cyano groups and intercalated K⁺ (mCNN), possessing extended visible‐light harvesting capacity and superior photocatalytic NRR activity (NH₃ yield: 3.42 mmol g^?1 h^?1). Experimental and theoretical studies suggest that the ‐C≡N in mCNN can be regenerated through a pathway analogous to Mars van Krevelen process with the aid of the intercalated K⁺. The results confirm that the regeneration of the cyano group not only enhances photocatalytic activity and sustains the catalytic cycle, but also stabilizes the photocatalyst.     

Preparation and Photocatalytic Activity of Mesoporous TiO2 Photocatalyst Co‐doped with Fe and H3PW12O40

The mesoporous titanium dioxide (MTiO₂) photocatalysts co‐doped with Fe and H₃PW₁₂O₄₀ were synthesized by template method using tetrabutyl titanate (Ti(OC₄H₉)₄), Fe(NO₃)k₃9H₂Oand H₃PW₁₂O₄₀ as precursors and Pluronic P123 as template. The as‐prepared photocatalyst was characterized by N₂ adsorption‐desorption measurements, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and UV‐vis adsorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl blue (MB) (50 mg/L) in an aqueous solution. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The results of MB photodecomposition showed that co‐doped mesoporous TiO₂ exhibited higher photocatalytic activities than un‐doped, single‐doped mesoporous TiO₂ under UV and visible light irradiation. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The synergistic effect of Fe and H₃PW₁₂O₄₀ co‐doping played an important role in improving the photocatalytic activity.     

Stable Heterometallic Cluster‐Based Organic Framework Catalysts for Artificial Photosynthesis

A series of stable heterometallic Fe₂M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO₂ and H₂O into HCOOH and O₂ without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO₂, and high‐valent Fe uses holes to oxidize H₂O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g^?1 h^?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction.     

Site‐Selected Doping of Upconversion Luminescent Er3+ into SrTiO3 for Visible‐Light‐Driven Photocatalytic H2 or O2 Evolution

A series of upconversion luminescent erbium‐doped SrTiO₃ (ABO₃‐type) photocatalysts with different initial molar ratios of Sr/Ti have been prepared by a facile polymerized complex method. Er³⁺ ions, which were gradually transferred from the A to the B site with increasing Sr/Ti, enabled the absorption of visible light and the generation of high‐energy excited states populated by upconversion processes. The local internal fields arising from the dipole moments of the distorted BO₆ octahedra promoted energy transfer from the high‐energy excited states of Er³⁺ with B‐site occupancy to the host SrTiO₃ and thus enhanced the band‐to‐band transition of the host SrTiO₃. Consequently, the erbium‐doped SrTiO₃ species with B‐site occupancy showed higher photocatalytic activity than those with A‐site occupancy for visible‐light‐driven H₂ or O₂ evolution in the presence of the corresponding sacrificial reagents. The results generally suggest that the introduction of upconversion luminescent agents into host semiconductors is a promising approach to simultaneously harnessing low‐energy photons and maintaining redox ability for photocatalytic H₂ and O₂ evolution and that the site occupancy of doped elements in ABO₃‐type perovskite oxides greatly determines the photocatalytic activity.     

Stabilization of Substituted Triazenide Oxides: Synthesis and X‐ray Structural Features of Polymeric Potassium 3‐(4‐carboxylatophenyl)‐1‐methyltriazene N‐oxide‐hydrate, {K[O2C‐C6H4‐N(H)NN(CH3)O]·4H2O}n

3‐(4‐carboxyphenyl)‐1‐methyltriazene N‐oxide reacts with KOH in methanol/pyridine to give {K[O₂C‐C₆H₄‐N(H)NN(CH₃)O]·4H₂O}_n, Potassium‐3‐(4‐carboxylatophenyl)‐1‐methyltriazene N‐oxide). The terminal carboxylato group of the anion does not interact with the cation. In the crystal lattice of {K(C₈H₈N₃O₃)·4H₂O}_n each three of the four water molecules interact with two potassium cations, every K⁺ ion being the centre of six bridging K···O interactions. Potassium cations interact further with the terminal N‐oxigen atom of single [C₈H₈N₃O₃]^? anions achieving two parallel {C₈H₈N₃O₃^?K⁺}_n chains, which are linked through water molecules. The resulting polymeric, one‐dimensional chain, is operated by a screw axis 2₁ parallel to the crystallographic direction [010], along and equidistant to the K⁺ centres. The coordination of the K⁺ centres involves a distortion of the boat conformation of elementary sulfur (S₈) with the ideal C_2v symmetry.     

Production of Hydrogen by Glycerol Photoreforming Using Binary Nitrogen–Metal‐Promoted N‐M‐TiO2 Photocatalysts

The need for renewable energy focuses attention on hydrogen obtained by using sustainable and green methods. The sustainable compound glycerol can be used for hydrogen production by heterogeneous photocatalysis. A novel approach involves the promotion of the TiO₂ photocatalyst with a binary combination of nitrogen and transition metal. We report the synthesis and spectroscopic characterization of the new N‐M‐TiO₂ photocatalysts (M=none, Cr, Co, Ni, Cu), and the photocatalytic reforming of glycerol to hydrogen under ambient conditions and near‐UV or visible light versus benchmark P25 TiO₂. In units of activity μmol m^?2 h^?1, N‐Ni‐TiO₂ is five‐fold more active than P25, and N‐Cu‐TiO₂ is 44‐fold more active. The photocatalytic activity of N‐M‐TiO₂ increases from Cr to Co and Ni, whereas the photoluminescence decreases; the change in activity is due to the modulation of charge recombination.