Enhanced localized dipole of Pt-Au single-site catalyst for solar water splitting.

Solar water splitting is regarded as holding great potential for clean fuels production. However, the efficiency of charge separation/transfer of photocatalysts is still too low for industrial application. This paper describes the synthesis of a Pt-Au binary single-site loaded g-C3N4 nanosheet photocatalyst inspired by the concept of the dipole. The existent larger charge imbalance greatly enhanced the localized molecular dipoles over adjacent Pt-Au sites in contrast to the unary counterparts. The superposition of molecular dipoles then further strengthened the internal electric field and thus promoted the charge transportation dynamics. In the modeling photocatalytic hydrogen evolution, the optimal Pt-Au binary site photocatalysts (0.25% loading) showed 4.9- and 2.3-fold enhancement of performance compared with their Pt and Au single-site counterparts, respectively. In addition, the reaction barrier over the Pt-Au binary sites was lowered, promoting the hydrogen evolution process. This work offers a valuable strategy for improving photocatalytic charge transportation dynamics by constructing polynary single sites.

Recent advances and new insights on the construction of photocatalytic systems for environmental disinfection.

Photocatalysis, as a sustainable and environmentally friendly green technology, has garnered widespread recognition and application across various fields. Especially its potential in environmental disinfection has been highly valued by researchers. This study commences with foundational research on photocatalytic disinfection technology and provides a comprehensive overview of its current developmental status. It elucidates the complexity of the interface reaction mechanism between photocatalysts and microorganisms, providing valuable insights from the perspectives of materials and microorganisms. This study reviews the latest design and modification strategies (Build heterojunction, defect engineering, and heteroatom doping) for photocatalysts in environmental disinfection. Moreover, this study investigates the research focuses and links in constructing photocatalytic disinfection systems, including photochemical reactors, light sources, and material immobilization technologies. It studies the complex challenges and influencing factors generated by different environmental media during the disinfection process. Simultaneously, a comprehensive review extensively covers the research status of photocatalytic disinfection concerning bacteria, fungi, and viruses. It reveals the observable efficiency differences caused by the microstructure of microorganisms during photocatalytic reactions. Based on these influencing factors, the economy and effectiveness of photocatalytic disinfection systems are analyzed and discussed. Finally, this study summarizes the current application status of photocatalytic disinfection products. The challenges faced by the synthesis and application of future photocatalysts are proposed, and the future development in this field is discussed. The potential for research and innovation has been further emphasized, with the core on improving efficiency, reducing costs, and strengthening the practical application of photocatalysis in environmental disinfection.

Exited State Absorption Upconversion Induced by Structural Defects for Photocatalysis with a Breakthrough Efficiency.

The nitrogen-deficient graphitic carbon nitride (g-C3 N4 ) has been prepared, a new excited state absorption (ESA) up-conversion mode is discovered, which is directly induced by structural defects, showing distinct chemical characteristics from those based on lanthanide ions and triplet states chromophores. The abundant N2C vacancies in g-C3 N4 nanosheets work as the crucial intermediate excitation states, which lead to g-C3 N4 upconverted emitting at the wavelength of 436 nm excited by the light with the wavelength of 800 nm. This process is proven to proceed via a two-photon involved ESA mode with a breakthrough quantum efficiency of 0.64 %. Further, we combine N2C vacancies enriched g-C3 N4 with In2 S3 and CdS, and successfully achieved an infrared light driven photocatalytic reactions. These findings offered a new family of up-conversion materials; more semiconductors with various structural defects are potential complementary members.

Novel Cerium-Based Sulfide Nano-Photocatalyst for Highly Efficient CO2 Reduction.

To address the environmental crisis caused by excessive emissions of CO2 , the development of effective photocatalysts for the conversion of CO2 into chemicals has emerged as one of the most promising strategies. Herein, beyond those well-studied materials, a rare-earth sulfide-based nanocrystal NaCeS2 is fabricated and investigated for efficient and selective conversion of CO2 into CO, where the role of Ce ions is crucial. Firstly, the hybridization of Ce 4f and Ce 5d orbitals contributes to the photoresponsive band structure of NaCeS2 . Secondly, due to the charge rearrangement supplied by the incompletely filled 4f orbitals of Ce ions, NaCeS2 exhibits excellent charge separation efficiency and CO2 adsorption affinity, reducing the energy barrier for the conversion from CO2 to CO. Moreover, a NaCeS2 -MoS2 heterostructure is also designed to further boost the electron transfer from the Mo site to the Ce site, which results in an improvement of the catalytic reduction yield from 7.24 to 23.42 µmol g-1 within 9 h (both better than TiO2 controls). This work offers a platform for the development of rare-earth-based photocatalysts for CO2 conversion.

Mechanistic Investigation of Alkali-Treated Photocatalytic CO2 Reduction: The Role of OH- and Metal Cations for Almost 100 % Selectivity of CO.

In this work, the modulation of activity and selectivity via photoreduction of carbon dioxide under simulated sunlight was achieved by treating P25 and P25/Pt NPs with KOH. It found that KOH treatment could significantly improve the overall conversion efficiency and switch the selectivity for CO. Photoelectric characterizations and CO2 -TPD demonstrated that the synergistic effect of K+ and OH- accelerated the separation and migration of photogenerated charges, and also improved CO2 adsorption level. Significantly, the K ions could act as active sites for CO2 adsorption and further activation. In situ FTIR measurements and DFT calculations confirmed that K+ enhanced the charge density of adjacent atoms and stabilize CO* groups, reducing the reaction energy barrier and inducing the switching of original CH4 to CO, which played a selective regulatory role. This study provides insights into the photocatalytic activity and selectivity of alkali-treated photocatalysts and facilitates the design of efficient and product-specific photocatalysis.

Conjugated π Electrons of MOFs Drive Charge Separation at Heterostructures Interface for Enhanced Photoelectrochemical Water Oxidation.

Photoanode material with high efficiency and stability is extensively desirable in photoelectrochemical (PEC) water splitting for green/renewable energy source. Herein, novel heterostructures is constructed via coating rutile TiO2 nanorods with metal organic framework (MOF) materials UiO-66 or UiO-67 (UiO-66@TiO2 and UiO-67@TiO2 ), respectively. The π electrons in the MOF linkers could increase the local electronegativity near the heterojunction interface due to the conjugation effect, thereby enhancing the internal electric field (IEF) at the heterojunction interface. The IEF could drive charge transfer following Z-scheme mechanism in the prepared heterostructures, inducing photogenerated charge separation efficiency increasing as 156% and 253% for the UiO-66@TiO2 and UiO-67@TiO2 , respectively. Correspondingly, the UiO-66@TiO2 and UiO-67@TiO2 enhanced the photocurrent density as approximate two- and threefolds compared with that of pristine TiO2 for PEC water oxidation in universal pH electrolytes. This work demonstrates an effective method of regulating the IEF of heterojunction toward further improved charge separation.

Efficient Electrochemical Nitrogen Fixation over Isolated Pt Sites.

Recently, ambient electrochemical N2 fixation has gained great attention. However, the commercial Pt-based electrocatalyst hardly shows its potential in this field. Herein, it is found that the isolated Pt sites anchored on WO3 nanoplates exhibit the optimum electrochemical NH3 yield rate (342.4 µg h-1 mg-1 Pt ) and Faradaic efficiency (31.1%) in 0.1 m K2 SO4 at -0.2 V versus RHE, which are about 11 and 15 times higher than their nanoparticle counterparts, respectively. The mechanistic analysis indicates that N2 conversion to NH3 follows an alternating hydrogenation pathway, and positively charged isolated Pt sites with special Pt-3O structure can favorably chemisorb and activate the N2 . Furthermore, the hydrogen evolution reaction can be greatly suppressed on isolated Pt sites decorated WO3 nanoplates, which guarantees the efficient going-on of nitrogen reduction reaction.

Band-Gap and Charge Transfer Engineering in Red Phosphorus-Based Composites for Enhanced Visible-Light-Driven H2 Evolution.

It is known that the low lifetime of photogenerated carriers is the main drawback of elemental photocatalysts. Therefore, a facile and versatile one-step strategy to simultaneously achieve the oxygen covalent functionalization of amorphous red phosphorus (RP) and in situ modification of CdCO3 is reported. This strategy endows RP with enhanced charge carrier separation ability and photocatalytic activity by coupling band-gap engineering and heterojunction construction. The as-prepared nCdCO3 /SO-RP (n=0.1, 0.25, 0.5, 1.0) composites exhibited excellent photocatalytic H2 evolution activity (up to 516.3 µmol g-1 h) from visible-light-driven water splitting (λ>400 nm), which is about 17.6 times higher than that of pristine RP. By experimental and theoretical investigations, the roles of surface oxygen covalent functionalization, that is, prolonging the lifetime of photogenerated carriers and inducing the negative shift of the conduction band potential, were studied in detail. Moreover, the charge transfer mechanism of these composites has also been proposed. In addition, these composites are stable and can be reused at least for three times without significant activity loss. This work may provide a good example of how to promote the activity of elemental photocatalysts by decorating their atomic structure.

Eosin Y sensitized BiPO4 nanorods for bi-functionally enhanced visible-light-driven photocatalysis.

In this work, we report a novel photocatalyst of Eosin Y dye sensitized BiPO4 nanorods via a low-temperature and impregnation adsorption method. It shows enhanced visible-light-driven photocatalytic activity for degrading methylene blue (MB) and 2,4-DCP compared to that of pristine BiPO4 nanorods. The mass ratio of Eosin Y/BiPO4 is varied from 5 wt% to 30 wt% and the optimum value is 15 wt%, showing 46.7 and 10.5 fold greater apparent reaction rates than pristine BiPO4. Moreover, all of the reduced MB was transformed into CO2 and H2O during the photocatalysis, showing the good mineralization ability (almost 100%) of the composite. Furthermore, the photocatalytic mechanism of the composite is also investigated here by the zeta potential, scavenger experiments, Electron Paramagnetic Resonance (EPR), Photoluminescence Spectroscopy (PL), and a series of electrochemical analyses. The results show that (i) e- is the main reactive species and (ii) Eosin Y coated and adsorbed on BiPO4, thus widening the response range to the visible light region and accelerating the charge separation/transfer, resulting in bi-functionally promoted activity.

The Role of Alkali Metal in α-MnO2 Catalyzed Ammonia-Selective Catalysis.

The unexpected phenomenon and mechanism of the alkali metal involved NH3 selective catalysis are reported. Incorporation of K+ (4.22 wt %) in the tunnels of α-MnO2 greatly improved its activity at low temperature (50-200 °C, 100 % conversion of NOx vs. 50.6 % conversion over pristine α-MnO2 at 150 °C). Experiment and theory demonstrated the atomic role of incorporated K+ in α-MnO2 . Results showed that K+ in the tunnels could form a stable coordination with eight nearby O sp 3 atoms. The columbic interaction between the trapped K+ and O atoms can rearrange the charge population of nearby Mn and O atoms, thus making the topmost five-coordinated unsaturated Mn cations (Mn5c , the Lewis acid sites) more positive. Therefore, the more positively charged Mn5c can better chemically adsorb and activate the NH3 molecules compared with its pristine counterpart, which is crucial for subsequent reactions.

Unraveling the Interfacial Charge Migration Pathway at the Atomic Level in a Highly Efficient Z-Scheme Photocatalyst.

A highly efficient Z-scheme photocatalytic system constructed with 1D CdS and 2D CoS2 exhibited high photocatalytic hydrogen-evolution activity of 5.54 mmol h-1 g-1 with an apparent quantum efficiency of 10.2 % at 420 nm. More importantly, its interfacial charge migration pathway was unraveled: The electrons are efficiently transferred from CdS to CoS2 through a transition atomic layer connected by Co-S5.8 coordination, thus resulting in more photogenerated carriers participating in surface reactions. Furthermore, the charge-trapping and charge-transfer processes were investigated by transient absorption spectroscopy, which gave an estimated charge-separation yield of approximately 91.5 % and a charge-separated-state lifetime of approximately (5.2±0.5) ns in CdS/CoS2 . This study elucidates the key role of interfacial atomic layers in heterojunctions and will facilitate the development of more efficient Z-scheme photocatalytic systems.

Isolated Platinum Atoms Stabilized by Amorphous Tungstenic Acid: Metal-Support Interaction for Synergistic Oxygen Activation.

Oxygen activation plays a crucial role in many important chemical reactions such as oxidation of organic compounds and oxygen reduction. For developing highly active materials for oxygen activation, herein, we report an atomically dispersed Pt on WO3 nanoplates stabilized by in situ formed amorphous H2 WO4 out-layer and the mechanism for activating molecular oxygen. Experimental and theoretical studies demonstrate that the isolated Pt atoms coordinated with oxygen atoms from [WO6 ] and water of H2 WO4 , consequently leading to optimized surface electronic configuration and strong metal-support interaction (SMSI). In exemplified reactions of butanone oxidation sensing and oxygen reduction, the atomic Pt/WO3 hybrid exhibits superior activity than those of Pt nanoclusters/WO3 and bare WO3 as well as enhanced long-term durability. This work will provide insight into the origin of activity and stability for atomically dispersed materials, thus promoting the development of highly efficient and durable single atom-based catalysts.

Converting Carbohydrates to Carbon-Based Photocatalysts for Environmental Treatment.

Carbohydrates in biomass can be converted to semiconductive hydrothermal carbonation carbon (HTCC), a material that contains plenty of sp2-hybridization structures. Under solar light illumination, HTCC generates photoexcited electrons, holes, and hydroxyl radicals. These species can be used for photocatalytic treatment such as water disinfection and degradation of organic pollutants. The photocatalytic activity of HTCC can be significantly enhanced by iodine doping. The enhancement mechanism is investigated by density functional theoretical calculations and electrochemical measurements. The iodine dopants twist and optimize the structures of the sp2-hybridization in HTCC, thereby favoring photon-induced excitation. Moreover, the iodine dopants facilitate the charge transfer between different sp2-hybridization structures, thus increasing the conductivity and activity of the HTCC. An added benefit is that the I-doped HTCC exhibits lower cytotoxic effect than the pure HTCC. In addition to monosaccharides (glucose), disaccharides (sucrose), and polysaccharides (starch), we have also transformed crops (e.g., rice), plants (e.g., grass), and even agricultural waste (e.g., straw) and animal waste (e.g., cow dung). The conversion of carbohydrates to HTCC may be considered as a "Trash to Treasure" approach. We believe this discovery will attract a lot of attention from researchers involved in environmental catalysis, waste recycling, and pollution treatment.

0D/2D Heterojunctions of Vanadate Quantum Dots/Graphitic Carbon Nitride Nanosheets for Enhanced Visible-Light-Driven Photocatalysis.

0D/2D heterojunctions, especially quantum dots (QDs)/nanosheets (NSs) have attracted significant attention for use of photoexcited electrons/holes due to their high charge mobility. Herein, unprecedent heterojunctions of vanadate (AgVO3 , BiVO4 , InVO4 and CuV2 O6 ) QDs/graphitic carbon nitride (g-C3 N4 ) NSs exhibiting multiple unique advances beyond traditional 0D/2D composites have been developed. The photoactive contribution, up-conversion absorption, and nitrogen coordinating sites of g-C3 N4 NSs, highly dispersed vanadate nanocrystals, as well as the strong coupling and band alignment between them lead to superior visible-light-driven photoelectrochemical (PEC) and photocatalytic performance, competing with the best reported photocatalysts. This work is expected to provide a new concept to construct multifunctional 0D/2D nanocomposites for a large variety of opto-electronic applications, not limited in photocatalysis.

An Elemental Phosphorus Photocatalyst with a Record High Hydrogen Evolution Efficiency.

Semiconductive property of elementary substance is an interesting and attractive phenomenon. We obtain a breakthrough that fibrous phase red phosphorus, a recent discovered modification of red phosphorus by Ruck et al., can work as a semiconductor photocatalyst for visible-light-driven hydrogen (H2 ) evolution. Small sized fibrous phosphorus is obtained by 1) loading it on photoinactive SiO2 fibers or by 2) smashing it ultrasonically. They display the steady hydrogen evolution rates of 633 µmol h(-1) g(-1) and 684 µmol h(-1) g(-1) , respectively. These values are much higher than previous amorphous P (0.6 µmol h(-1) g(-1) ) and Hittorf P (1.6 µmol h(-1) g(-1) ). Moreover, they are the highest records in the family of elemental photocatalysts to date. This discovery is helpful for further understanding the semiconductive property of elementary substance. It is also favorable for the development of elemental photocatalysts.

Red Phosphorus: An Earth-Abundant Elemental Photocatalyst for "Green" Bacterial Inactivation under Visible Light.

Earth-abundant red phosphorus was found to exhibit remarkable efficiency to inactivate Escherichia coli K-12 under the full spectrum of visible light and even sunlight. The reactive oxygen species (•OH, •O2(-), H2O2), which were measured and identified to derive mainly from photogenerated electrons in the conduction band using fluorescent probes and scavengers, collectively contributed to the good performance of red phosphorus. Especially, the inactivated-membrane function enzymes were found to be associated with great loss of respiratory and ATP synthesis activity, the kinetics of which paralleled cell death and occurred much earlier than those of cytoplasmic proteins and chromosomal DNA. This indicated that the cell membrane was a vital first target for reactive oxygen species oxidation. The increased permeability of the cell membrane consequently accelerated intracellular protein carboxylation and DNA degradation to cause definite bacterial death. Microscopic analyses further confirmed the cell destruction process starting with the cell envelope and extending to the intracellular components. The red phosphorus still maintained good performance even after recycling through five reaction cycles. This work offers new insight into the exploration and use of an elemental photocatalyst for "green" environmental applications.

Highly efficient and 100 % selectivity of CO generation via CO2 Photoreduction over a novel CsBr@CuBr2 Heterojunction.

To address the global challenge posed by excessive carbon dioxide emissions, our research pioneers the transformation of CO2 into valuable hydrocarbon fuels. Central to this approach is the innovation of photocatalysts, engineered to exhibit exceptional photoresponse characteristics. In this research, the CsBr@CuBr2 photocatalyst was innovatively synthesized through a straightforward and effective one-pot method. The catalyst displayed remarkable efficacy, achieving a CO2 photoreduction rate of 201.47 µmol g-1 within just 4 h. The incorporation of CsBr into CuBr2 effectively captures excited-state electrons, thereby significantly enhancing charge separation efficiency. Utilizing in situ DRIFTS and DFT theoretical analysis, the experiment reveals the complex process of CO2 photoreduction to CO. The results of this experiment provide breakthrough insights for the systematic design of metal bromide heterostructures, which possess robust CO2 adsorption/activation potential and notable stability.

Boosting the photocatalytic activation of molecular oxygen and photodegradation of tetracycline: The role of interfacial synergistic effect of cocatalyst and dopants.

Utilizing reactive oxygen species (ROS), which are generated by the activation of molecular oxygen (O2) in oxidation reaction, is a promising method for pollutant degradation. However, it is limited by the commonly low efficiency of O2 activation and carrier separation. Herein, as a model system, Ag cocatalyst and Cl doping modified g-C3N4 (Ag/Cl-CN) was constructed to improve the ability of O2 activation. Results showed that Ag/Cl-CN could effectively convert more O2 into ROS than pristine g-C3N4 (CN), and individually decorated CN (Ag-CN and Cl-CN). A series of experiments and DFT calculations revealed that the deposition of Ag could promote charge separation resulting in more charges accumulated around O2 and the introduction of Cl led to a stronger adsorption capacity for O2. Therefore, due to the synergistic effect of Ag cocatalyst and Cl dopant, Ag/Cl-CN generated higher concentrations of O2- and displayed much better activity for photocatalytic degradation of tetracycline (TC) than CN, Ag-CN and Cl-CN.

Photoassisted highly efficient activation of persulfate over a single-atom Cu catalyst for tetracycline degradation: Process and mechanism.

A single-atomic-site Cu catalyst (SAS-Cu) supported on carbon nitride (CN) material was synthesized by a pyrolyzing coordinated polymer (PCP) strategy. The introduction of a single-atomic Cu site improved the charge transfer and separation efficiency. The reaction rate constant of SAS-Cu1.0 is 4.5 times higher than that of CN. Under the condition of only 0.1 mM sodium persulfate (PS) and 0.1 g/L catalyst, the removal rate of tetracycline (TC) reached 82.5% after 30 min of LED illumination, which greatly improved the utilization of oxidant. Mechanistic analysis shows that there are free radical (•O2-, SO4•-, •OH) and nonradical pathways (1O2 and direct electron transfer) in the system, and they have synergistic effect. Density functional theory (DFT) calculations show that SAS-Cu1.0 can optimize the adsorption and activation of PS. This work illustrates the application value of SAC combined with activated persulfate and the low energy consumption of the LED light in the field of environment, which provides a new strategy for reducing the salinity and treatment cost of treated water.

Identification of the Stable Pt Single Sites in the Environment of Ions: From Mechanism to Design Principle.

For single-atom (SA)-based catalysis, it is urgent to understand the nature and dynamic evolution of SA active sites during the reactions. In this work, an example of Pt SA-Zn0.5 Cd0.5 S (Pt SA-ZCS) is found to display interesting phenomena when facing the Brownian collision of ions in aqueous photocatalysis. Via synchrotron radiation, surface techniques, microscopy, and theory calculations, the results show that two kinds of Pt sites exist: PtZn-sub -S3 (Pt substituting the Zn site) and Ptads -S2 (Pt adsorbing on the surface). In Na2 S, the S2- can coordinate with Pt atoms and peel them from the Ptads -S2 sites, but leaves more stable PtZn-sub -S3 sites, bringing a low but stable catalytic activity (19.40 mmol g-1 h-1 ). Meanwhile, in ascorbic acid, the ascorbic acid ions show less complex ability with Pt atoms, but can decrease the migration barrier of Ptads -S2 sites (67.18 down to 35.96 mmol g-1 h-1 , 52.03% drop after 6 h). Therefore, the Ptads -S2 sites gradually aggregate into nanoclusters, bringing a high but decayed catalytic activity. Moreover, a Pt SA-ZCS-Sulfur composite is designed mainly covered by PtZn-sub -S3 sites accordingly (max: 79.09 mmol g-1 h-1 , 5% drop after 6 h and QE: 14.0% at 420 nm), showing a beneficial strategy "from mechanism to design principle."