Water-Resistance-Based S-Scheme Heterojunction for Deep Mineralization of Toluene.

Deep mineralization of low concentration toluene (C7 H8 ) is one of the most significant but challenging reactions in photocatalysis. It is generally assumed that hydroxyl radicals (⋅OH) as the main reactive species contribute to the enhanced photoactivity, however, it remains ambiguous at this stage. Herein, a S-scheme ZnSn(OH)6 -based heterojunction with AlOOH as water resistant surface layer is in situ designed for tuning the free radical species and achieving deep mineralization of C7 H8 . By employing a combination of in situ DRIFTS and materials characterization techniques, we discover that the dominant intermediates such as benzaldehyde and benzoic acid instead of toxic phenols are formed under the action of holes (h+ ) and superoxide radicals (⋅O2 - ). These dominant intermediates turn out to greatly decrease the ring-opening reaction barrier. This study offers new possibilities for rationally tailoring the active species and thus directionally producing dominant intermediates via designing water resistant surface layer.

Surface Hydrogen Bond-Induced Oxygen Vacancies of TiO2 for Two-Electron Molecular Oxygen Activation and Efficient NO Oxidation.

Defect engineering can provide a feasible approach to achieving ambient molecular oxygen activation. However, conventional surface defects (e.g., oxygen vacancies, OVs), featured with the coordinatively unsaturated metal sites, often favor the reduction of O2 to •O2- rather than O22- via two-electron transfer, hindering the efficient pollutant removal with high electron utilization. Herein, we demonstrate that this bottleneck can be well discharged by modulating the electronic structure of OVs via phosphorization. As a proof of concept, TiO2 nanoparticles are adopted as a model material for NaH2PO2 (HP) modification, in which HP induces the formation of OVs via weakening the Ti-O bonds through the hydrogen bond interactions. Additionally, the formed Ti-O-P covalent bond refines the electronic structure of OVs, which enables rapid electron transfer for two-electron molecular oxygen activation. As exemplified by NO oxidation, HP-modified TiO2 with abundant OVs achieved complete NO removal with high selectivity for benign nitrate, superior to that of pristine TiO2. This study highlights a promising approach to regulate the O2 activation via an electronic structure modulation and provides fresh insights into the rational design of a photocatalyst for environmental remediation.

Microwave assisted synthesis of PQ-GDY@NH2-UIO-66(Zr) for improved photocatalytic removal of NOx under visible light.

Pyrazinoquinoxaline-based graphdiyne (PQ-GDY) contains a fixed number of sp-sp2 hybridized carbon atoms and pyrazine-like sp2 hybridized N atoms. In this paper, NH2-UIO-66(Zr) on PQ-GDY substrate was successfully constructed with the help of microwave-assisted heating. PQ-GDY surface acts as a microwave antenna under microwave irradiation to rapidly absorb microwave energy and form hot spots (hot spot effect), which facilitates the formation of well-dispersed NH2-UIO-66(Zr) with good crystallinity. Transient absorption spectra show that high hole transport property of PQ-GDY can accelerate the migration of photogenerated holes from NH2-UIO-66(Zr) to PQ-GDY and greatly reduce the recombination rate of photogenerated electrons and holes due to the strong interaction between PQ-GDY and NH2-UIO-66(Zr). Under visible light (λ ≥ 420 nm), PQ-GDY@NH2-UIO-66(Zr) shows high photocatalytic stability and high NOx removal rate up to 74%, which is 44% higher than that of primitive NH2-UIO-66(Zr). At the same time, it inhibits the formation of toxic by-products (NO2) and limits its concentration to a low level.

Hydroxyl Radical-Mediated Efficient Photoelectrocatalytic NO Oxidation with Simultaneous Nitrate Storage Using A Flow Photoanode Reactor.

The selective conversion of dilute NO pollutant into low-toxic product and simultaneous storage of metabolic nitrogen for crop plants remains a great challenge from the perspective of waste management and sustainable chemistry. This study demonstrates that this bottleneck can be well tackled by refining the reactive oxygen species (ROS) on Ni-modified NH2 -UiO-66(Zr) (Ni@NU) using nickel foam (NF) as a three-dimensional (3D) substrate through a flow photoanode reactor via the gas-phase photoelectrocatalysis. By rationally refining the ROS to ⋅OH, Ni@NU/NF can rapidly eliminate 82 % of NO without releasing remarkable NO2 under a low bias voltage (0.3 V) and visible light irradiation. The abundant mesoporous pores on Ni@NU/NF are conducive to the diffusion and storage of the formed nitrate, which enables the progressive conversion NO into nitrate with selectivity over 99 % for long-term use. Through calculation, 90 % of NO could be recovered as the nitrate species, indicating that this state-of-the-art strategy can capture, enrich and recycle the pollutant N source from the atmosphere. This study offers a new perspective of NO pollutant treatment and sustainable nitrogen exploitation, which may possess great potential to the development of highly efficient air purification systems for industrial and indoor NOx control.

Singlet Oxygen and Mobile Hydroxyl Radicals Co-operating on Gas-Solid Catalytic Reaction Interfaces for Deeply Oxidizing NOx.

Learning from the important role of porphyrin-based chromophores in natural photosynthesis, a bionic photocatalytic system based on tetrakis (4-carboxyphenyl) porphyrin-coupled TiO2 was designed for photo-induced treating low-concentration NOx indoor gas (550 parts per billion), achieving a high NO removal rate of 91% and a long stability under visible-light (λ ≥ 420 nm) irradiation. Besides the great contribution of the conventional •O2- reactive species, a synergic effect between a singlet oxygen (1O2) and mobile hydroxyl radicals (•OHf) was first illustrated for removing NOx indoor gas (1O2 + 2NO → 2NO2, NO2 + •OHf → HNO3), inhibiting the production of the byproducts of NO2. This work is helpful for understanding the surface mechanism of photocatalytic NOx oxidation and provides a new perspective for the development of highly efficient air purification systems.

Gas-Phase Photoelectrocatalytic Oxidation of NO via TiO2 Nanorod Array/FTO Photoanodes.

Most photoelectrocatalytic (PEC) reactions are performed in the liquid phase for convenient electron transfer in an electrolyte solution. Herein, a novel PEC reactor involving a tandem combination of TiO2 nanorod array/fluorine-doped tin oxide (TiO2-NR/FTO) working electrodes and an electrochemical auxiliary cell was constructed to drive the highly efficient PEC oxidation of indoor gas (NOx). With the aid of a low bias voltage (0.3 V), the as-formed PEC reactor exhibited an 80% removal rate for oxidizing NO (500 ppb) under light irradiation, which is much higher than that of the traditional photocatalytic (PC) process. Upon being irradiated by light, the photogenerated electrons are quickly separated from the holes and transferred to the counter electrode (Pt) owing to the applied bias voltage, leaving photogenerated holes in the TiO2-NR/FTO electrode for oxidizing NO molecules. Moreover, both dry and humid NO could be effectively removed by the tandem TiO2-NR/FTO-based gas-phase PEC reactor, indicating that the NO molecules could also be directly oxidized by photogenerated holes in addition to hydroxyl radicals. The presence of trace amounts of water could promote the PEC oxidation of NO owing to the formation of hydroxyl radicals induced by reactions between the water and holes, which could further oxidize NO. This PEC reactor offers an energy-saving, environmentally friendly, and efficient route to treat air polluted with low concentrations of gases (NOx and SOx).

MOFs Conferred with Transient Metal Centers for Enhanced Photocatalytic Activity.

Highly effective photocatalysts for the hydrogen-evolution reaction were developed by conferring the linkers of NH2 -MIL-125(Ti), a metal-organic framework (MOF) constructed from TiOx clusters and 2-aminoterephthalic acid (linkers), with active copper centers. This design enables effective transfer of electrons from the linkers to the transient Cu2+ /Cu+ centers, leading to 7000-fold and 27-fold increase of carrier density and lifetime of photogenerated charges, respectively, as well as high-rate production of H2 under visible-light irradiation. This work provides a novel design of a photocatalyst for hydrogen evolution using non-noble Cu2+ /Cu+ as co-catalysts.

Gas-Phase Photoelectrocatalysis for Breaking Down Nitric Oxide.

Photoelectrocatalysis (PEC) produces high-efficiency electron-hole separation by applying a bias voltage between semiconductor-based electrodes to achieve high photocatalytic reaction rates. However, using PEC to treat polluted gas in a gas-phase reaction is difficult because of the lack of a conductive medium. Herein, we report an efficient PEC system to oxidize NO gas by using parallel photoactive composites (TiO2 nanoribbons-carbon nanotubes) coated on stainless-steel mesh as photoanodes in a gas-phase chamber and Pt foil as the working electrode in a liquid-phase auxiliary cell. Carbon nanotubes (CNTs) were utilized as conductive scaffolds to enhance the interaction between TiO2 and stainless-steel skeletons for accelerated photogenerated electron transfer. Such a PEC system exhibited super-high performance for the treatment of indoor NO gas (550 ppb) with high selectivity for nitrate under UV-light irradiation owing to the conductive, intertwined network structure of the photoanode, fast photocarrier separation, and longer photogenerated hole lifetime. The photogenerated holes were proven to be the most important active sites for directly driving PEC oxidation of indoor NO gas, even in the absence of water vapor. This work created an efficient PEC air-purification filter for treating indoor polluted air under ambient conditions.

Efficient Photocatalytic Fuel Cell via Simultaneous Visible-Photoelectrocatalytic Degradation and Electricity Generation on a Porous Coral-like WO3/W Photoelectrode.

Photocatalytic fuel cells (PFCs) have proven to be effective for generating electricity and degrading pollutants with a goal to resolve environmental and energy problems. However, the degradation of persistent organic pollutants (POPs), such as perfluorooctanoic acid (PFOA), remains challenging. In the present work, a porous coral-like WO3/W (PCW) photoelectrode with a well-designed energy band structure was used for the photoelectrocatalytic degradation of POPs and the simultaneous generation of electricity. The as-constructed bionic porous coral-like nanostructure greatly improved the light-harvesting capacity of the PCW photoelectrode. A maximum photocurrent density (0.31 mA/cm2) under visible light (λ > 420 nm) irradiation and a high incident photon conversion efficiency (IPCE) value (5.72% at 420 nm) were achieved. Because of the unique porous coral-like structure, the suitable energy band position, and the strong oxidation ability, this PCW photoelectrode-based PFC system exhibited a strong ability for simultaneous photoelectrocatalytic degradation of PFOA and electricity generation under visible-light irradiation, with a power output of 0.0013 mV/cm2 using PFOA as the fuel. This work provides a promising way to construct a reliable PFC using highly toxic POPs to generate electricity.

Photoelectrocatalytic reduction of CO2 to methanol over a photosystem II-enhanced Cu foam/Si-nanowire system.

A solar-light double illumination photoelectrocatalytic cell (SLDIPEC) was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II (PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires (Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate (41.94mmol/hr), owing to fast electron transfer from PS-II to Cu foam. Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage (0.5V), and a suitable conduction band potential of Si (-0.6eV) allowed CO2 to be easily reduced to CH3OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2 (8.03mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.

Copper Nanowires: A Substitute for Noble Metals to Enhance Photocatalytic H2 Generation.

Microwave-assisted hydrothermal approach was developed as a general strategy to decorate copper nanowires (CuNWs) with nanorods (NRs) or nanoparticles (NPs) of metal oxides, metal sulfides, and metal organic frameworks (MOFs). The microwave irradiation induced local "super hot" dots generated on the CuNWs surface, which initiated the adsorption and chemical reactions of the metal ions, accompanied by the growth and assembly of NPs building blocks along the metal nanowires' surfaces. This solution-processed approach enables the NRs (NPs) @CuNWs hybrid structure to exhibit three unique characteristics: (1) high coverage density of NRs (NPs) per NWs with the morphology of NRs (NPs) directly growing from the CuNWs core, (2) intimate contact between CuNWs and NRs (NPs), and (3) flexible choices of material composition. Such hybrid structures also increased light absorption by light scattering. In general, the TiO2/CuNWs showed excellent photocatalytic activity for H2 generation. The corresponding hydrogen production rate is 5104 µmol h(-1) g(-1) with an apparent quantum yield (AQY) of 17.2%, a remarkably high AQY among the noble-metal free TiO2 photocatalysts. Such performance may be associated with the favorable geometry of the hybrid system, which is characterized by a large contact area between the photoactive materials (TiO2) and the H2 evolution cocatalyst (Cu), the fast and short diffusion paths of photogenerated electrons transferring from the TiO2 to the CuNWs. This study not only shows a possibility for the utilization of low cost copper nanowires as a substitute for noble metals in enhanced solar photocatalytic H2 generation but also exhibits a general strategy for fabricating other highly active H2 production photocatalysts by a facile microwave-assisted solution approach.

Hierarchical Nanostructured WO3 with Biomimetic Proton Channels and Mixed Ionic-Electronic Conductivity for Electrochemical Energy Storage.

Protein channels in biologic systems can effectively transport ions such as proton (H(+)), sodium (Na(+)), and calcium (Ca(+)) ions. However, none of such channels is able to conduct electrons. Inspired by the biologic proton channels, we report a novel hierarchical nanostructured hydrous hexagonal WO3 (h-WO3) which can conduct both protons and electrons. This mixed protonic-electronic conductor (MPEC) can be synthesized by a facile single-step hydrothermal reaction at low temperature, which results in a three-dimensional nanostructure self-assembled from h-WO3 nanorods. Such a unique h-WO3 contains biomimetic proton channels where single-file water chains embedded within the electron-conducting matrix, which is critical for fast electrokinetics. The mixed conductivities, high redox capacitance, and structural robustness afford the h-WO3 with unprecedented electrochemical performance, including high capacitance, fast charge/discharge capability, and very long cycling life (>50,000 cycles without capacitance decay), thus providing a new platform for a broad range of applications.

Highly efficient and stable Au/CeO2-TiO2 photocatalyst for nitric oxide abatement: potential application in flue gas treatment.

In the present work, highly efficient and stable Au/CeO2-TiO2 photocatalysts were prepared by a microwave-assisted solution approach. The Au/CeO2-TiO2 composites with optimal molar ratio of Au/Ce/Ti of 0.004:0.1:1 delivered a remarkably high and stable NO conversion rate of 85% in a continuous flow reactor system under simulated solar light irradiation, which far exceeded the rate of 48% over pure TiO2. The tiny Au nanocrystals (∼1.1 nm) were well stabilized by CeO2 via strong metal-support bonding even it was subjected to calcinations at 550 °C for 6 h. These Au nanocrystals served as the very active sites for activating the molecule of nitric oxide and reducing the transmission time of the photogenerated electrons to accelerate O2 transforming to reactive oxygen species. Moreover, the Au-Ce(3+) interface formed and served as an anchoring site of O2 molecule. Then more adsorbed oxygen could react with photogenerated electrons on TiO2 surfaces to produce more superoxide radicals for NO oxidation, resulting in the improved efficiency. Meanwhile, O2 was also captured at the Au/TiO2 perimeter site and the NO molecules on TiO2 sites were initially delivered to the active perimeter site via diffusion on the TiO2 surface, where they assisted O-O bond dissociation and reacted with oxygen at these perimeter sites. Therefore, these finite Au nanocrystals can consecutively expose active sites for oxidizing NO. These synergistic effects created an efficient and stable system for breaking down NO pollutants. Furthermore, the excellent antisintering property of the catalyst will allow them for the potential application in photocatalytic treatment of high-temperature flue gas from power plant.

Promoting Proton Donation through Hydrogen Bond Breaking on Carbon Nitride for Enhanced H2O2 Photosynthesis.

Photocatalytic H2O2 production has attracted much attention as an alternative way to the industrial anthraquinone oxidation process but is limited by the weak interaction between the catalysts and reactants as well as inefficient proton transfer. Herein, we report on a hydrogen-bond-broken strategy in carbon nitride for the enhancement of H2O2 photosynthesis without any sacrificial agent. The H2O2 photosynthesis is promoted by the hydrogen bond formation between the exposed N atoms on hydrogen-bond-broken carbon nitride and H2O molecules, which enhances proton-coupled electron transfer and therefore the photocatalytic activity. The exposed N atoms serve as proton buffering sites for the proton transfer from H2O molecules to carbon nitride. The H2O2 photosynthesis is also enhanced through the enhanced adsorption and reduction of O2 gas toward H2O2 on hydrogen-bond-broken carbon nitride because of the formation of nitrogen vacancies (NVs) and cyano groups after the intralayer hydrogen bond breaking on carbon nitride. A high light-to-chemical conversion efficiency (LCCE) value of 3.85% is achieved. O2 and H2O molecules are found to undergo a one-step two-electron reduction pathway by photogenerated hot electrons and a four-electron oxidation process to produce O2 gas, respectively. Density functional theory (DFT) calculations validate the O2 adsorption and reaction pathways. This study elucidates the significance of the hydrogen bond formation between the catalyst and reactants, which greatly increases the proton tunneling dynamics.

Mesoporous amorphous non-noble metals as versatile substrates for high loading and uniform dispersion of Pt-group single atoms.

Atomically dispersed Pt-group metals are promising as nanocatalysts because of their unique geometric structures and ultrahigh atomic utilization. However, loading isolated Pt-group metals in single-atom alloys (SAAs) with distinctive bimetallic sites is challenging. In this study, we present amorphous mesoporous Ni boride (Ni-B) as an ideal substrate to uniformly disperse Pt atoms with tunable loadings (1.7 to 12.2 wt %). The effect of the morphology, composition, and crystal phase of the Ni-B host on the growth and dispersion of Pt atoms is discussed. The resulting amorphous Pt-Ni-B mesoporous nanospheres exhibit superior electrocatalytic H2 evolution performance in acidic media. This strategy holds the potential to synthesize a diverse library of mesoporous amorphous Pt-group SAAs, by leveraging functional amorphous nanostructured 3d transition-metal borides as substrates, thereby proposing a comprehensive strategy to control atomically dispersed Pt-group metals.

Activation of chloride by oxygen vacancies-enriched TiO2 photoanode for efficient photoelectrochemical treatment of persistent organic pollutants and simultaneous H2 generation.

Photoelectrochemical (PEC) activation of chloride ions (Cl-) to degrade persistent organic pollutants (POPs) is a promising strategy for the treatment of industrial saline organic wastewater. However, the wide application of this technology is greatly restricted due to the general photoanode activation of Cl- with poor capability, the propensity to produce toxic by-products chlorates, and the narrow pH range. Herein, oxygen vacancies-enriched titanium dioxide (Ov-TiO2) photoanode is explored to strongly activate Cl- to drive the deep mineralization of POPs wastewater in a wide pH range (2-12) with simultaneous production of H2. More importantly, nearly no toxic by-product of chlorates was produced during such PEC-Cl system. The degradation efficiency of 4-CP and H2 generation rate by Ov-TiO2 were 99.9% within 60 min and 198.2 µmol h-1 cm-2, respectively, which are far superior to that on the TiO2 (33.1% within 60 min, 27.5 µmol h-1 cm-2) working electrode. DFT calculation and capture experiments revealed that Ov-TiO2 with abundant oxygen vacancies is conducive to the activation of Cl- to produce more reactive chlorine species, evidenced by its high production of free chlorine (48.7 mg L-1 vs 7.5 mg L-1 of TiO2). The as-designed PEC-Cl system in this work is expected to realize the purification of industrial saline organic wastewater coupling with green energy H2 evolution.

Modulating the Active Hydrogen Adsorption on Fe─N Interface for Boosted Electrocatalytic Nitrate Reduction with Ultra-Long Stability.

The electrocatalytic reduction of nitrate (NO3 - ) to nitrogen (N2 ) is an environmentally friendly approach for efficient N-cycle management (toward a nitrogen-neutral cycle). However, poor catalyst durability and the competitive hydrogen evolution reaction significantly impede its practical application. Interface-chemistry engineering, utilizing the close relationship between the catalyst surface/interface microenvironment and electron/proton transfer process, has facilitated the development of catalysts with high intrinsic activity and physicochemical durability. This study reports the synthesis of a nitrogen-doped carbon-coated rice-like iron nitride (RL-Fe2 N@NC) electrocatalyst with excellent electrocatalytic nitrate-reduction reaction activity (high N2 selectivity (≈96%) and NO3 - conversion (≈86%)). According to detailed mechanistic investigations by in situ tests and theoretical calculations, the strong hydrogenation ability of iron nitride and enhanced nitrate enrichment of the system synergistically contribute to the rapid hydrogenation of nitrogen-containing species, increasing the intrinsic activity of the catalyst and reducing the occurrence of the competing hydrogen-evolution side reaction. Moreover, RL-Fe2 N@NC shows excellent stability, retaining good NO3 - -to-N2 electrocatalysis activity for more than 40 cycles (one cycle per day). This paper could guide the interfacial design of Fe-based composite nanostructures for electrocatalytic nitrate reduction, facilitating a shift toward nitrogen neutrality.

Synthesis of ultralong copper nanowires for high-performance transparent electrodes.

Cu nanowires hold great promise for the fabrication of low-cost transparent electrodes. However, their current synthesis is mainly performed in aqueous media with poor nanowire dispersibility. We report herein the novel synthesis of ultralong single-crystalline Cu nanowires with excellent dispersibility, providing an excellent candidate material for high-performance transparent electrode fabrication.

Microwave-induced synthesis of porous single-crystal-like TiO2 with excellent lithium storage properties.

Porous anatase TiO(2) single crystal architectures with large specific surface area and remarkable crystalline phase-stability were fabricated via a green microwave-assisted process. Ionic liquid was chosen as both an essential structure-directing agent for the formation of the {001} facets exposed TiO(2) and an etching agent source for selective erosion of the exposed {001} facets, leading to robust porous framework with exposed {101} facets. These porous anatase single crystals were thermally stable up to 800 °C, indicating excellent structure stability. The product showed stable cyclability at high current rate, better reversibility, and high Coulumbic efficiency of 100% for lithium storage.

Dual-emitting metal-organic frameworks for ratiometric fluorescence detection of fluoride and Al3+ in sequence.

Fluoride (F-) and Al3+ are two common ions existing in drinking water and natural water bodies. Excessive intake of F- can lead to serious health issues such as fluorosis and bone diseases while accumulated consumption of Al3+ may cause neurotoxicity-based diseases. Developing a fast, reliable, and sensitive sensor for visually detecting both F- and Al3+ is of great significance. In the present work, a ratiometric fluorescence sensor was constructed by incorporating rhodamine B (RhB) in situ into a zirconium-based metal-organic framework, UiO-66-NH2. The obtained nanocomposite UiO-66-NH2@RhB exhibited similar octahedral structure to UiO-66-NH2 with high BET surface area, and showed two emission peaks at 450 nm and 585 nm. The blue fluorescence from UiO-66-NH2 was enhanced by the addition of F- while subsequent Al3+ addition diminished the increased fluorescence intensity, and the red emission from RhB as the reference remained unchangeable to improve the detection precision. Under optimal conditions, detection of limits as low as 1.55 µM for F- and 0.54 µM for Al3+ in aqueous solution were achieved with good selectivity. High recoveries in drinking water samples were also acquired, showing potential applications of this ratiometric fluorescence sensor for practical evaluation of F- and Al3+.