An all-in-one FeOx-rGO sponge fabricated by solid-phase microwave thermal shock for water evaporation and purification.

Developing high-efficiency photothermal seawater desalination devices is of significant importance in addressing the shortage of freshwater. Despite much effort made into photothermal materials, there is an urgent need to design a rapidly synthesized photothermal evaporator for the comprehensive purification of complex seawater. Therefore, we report on all-in-one FeOx-rGO photothermal sponges synthesized via solid-phase microwave thermal shock. The narrow band gap of the semiconductor material Fe3O4 greatly reduces the recombination of electron-hole pairs, enhancing non-radiative relaxation light absorption. The abundant π orbitals in rGO promote electron excitation and thermal vibration between the lattices. Control of the surface hydrophilicity and hydrophobicity promotes salt resistance while simultaneously achieving the purification of various complex polluted waters. The optimized GFM-3 sponge exhibitedan enhanced photothermal conversion rate of 97.3% and a water evaporation rate of 2.04 kg/(m2·hr), showing promising synergistic water purification properties. These findings provide a highly efficient photothermal sponge for practical applicationsof seawater desalination and purification,as well as develop a super-rapid processing methodology for evaporation devices.

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.

Surface, Interface and Structure Optimization of Metal-Organic Frameworks: Towards Efficient Resourceful Conversion of Industrial Waste Gases.

Industrial waste gas emissions from fossil fuel over-exploitation have aroused great attention in modern society. Recently, metal-organic frameworks (MOFs) have been developed in the capture and catalytic conversion of industrial exhaust gases such as SO2 , H2 S, NOx , CO2 , CO, etc. Based on these resourceful conversion applications, in this review, we summarize the crucial role of the surface, interface, and structure optimization of MOFs for performance enhancement. The main points include (1) adsorption enhancement of target molecules by surface functional modification, (2) promotion of catalytic reaction kinetics through enhanced coupling in interfaces, and (3) adaptive matching of guest molecules by structural and pore size modulation. We expect that this review will provide valuable references and illumination for the design and development of MOF and related materials with excellent exhaust gas treatment performance.

Vacancy-rich BiO2-x as a highly-efficient persulfate activator under near infrared irradiation for bacterial inactivation and mechanism study.

This study, for the first time, developed a novel defective BiO2-x based collaborating system, where the near-infrared light (NIR) irradiation (λ > 700 nm) initiated persulfate activation and photocatalytic bacterial inactivation simultaneously. Vacancy-rich BiO2-x nanoplates possessed impressive NIR absorption and firstly realized persulfate activation under NIR irradiation. In this collaborating system, on one hand, the persulfate can be transformed into sulfate radicals through light/heat activation mode directly, which would be enhanced by the presence of vacancy-rich BiO2-x owing to its outstanding light and heat absorption ability. On the other hand, the photogenerated electrons can further efficiently react with persulfate and form sufficient reactive sulfate radicals. The sulfate radicals, synergizing with other reactive species (O2-, h+, etc.), achieved a 7-log Escherichia coli inactivation within 40 min. The systematic investigation of inactivation mechanism revealed that the reactive species caused the dysfunction of cellular respiration, ATP synthesis and bacterial membrane, followed by the severely oxidative damage to the antioxidative SOD and CAT enzymes and the generation of carbonylated protein. The final leakage of DNA and RNA implied the lethal damage to the bacteria cells. This work provided a new insight into the persulfate associated NIR driven remediation technology of controlling microbial contaminants.

Self-Suspended Photothermal Microreactor for Water Desalination and Integrated Volatile Organic Compound Removal.

Steam generation and photocatalytic degradation of organic pollutants based on solar light are regarded as two important strategies for addressing the water scarcity issues. The water evaporation efficiency was greatly inhibited by the high cost, low stability, and low efficiencies of solar light absorption and photothermal conversion of photothermal materials. Moreover, volatile organic compounds (VOCs) are easily volatilized and enriched in as-distilled water during the photothermal process. Inspired by the structure of biomass materials in nature, a bifunctional solar light-driven steam generation and VOC removal microreactor was explored by coating commercial TiO2 (P25) powders on a carbonized biomass waste Flammulina. With the 3D aligned porous carbon architectures, this microreactor exhibited both a high water evaporation rate (37.0 kg m-2 h-1) and a high energy conversion efficiency (91.2%) under simulated sunlight irradiation (light intensity = 25.5 kW m-2). A high VOC removal rate (80.9% in 40 min) was also achieved during the steam generation process via choosing phenol as the probe pollutant molecules. The nature-inspired designing concept and bifunctional microreactor in this study may open up a new strategy for producing clean distilled water from seawater with an efficient removal of VOCs.

Solid-Phase Microwave Reduction of WO3 by GO for Enhanced Synergistic Photo-Fenton Catalytic Degradation of Bisphenol A.

The synergistic photocatalytic Fenton reaction is a powerful advanced oxidation technique for the degradation of persistent organic pollutants. However, microwave-induced thermal effects on the formation of novel structures facilitating the photocatalytic degradation have been rarely reported. Herein, a two-step microwave thermal strategy was developed to synthesize a new hybrid catalyst comprising defective WO3-x nanowires coupled with reduced graphene oxides (rGOs). Conventionally, microwave methods could induce superhot spots on the GO surface, resulting in the site-specific crystallization and oriented growth of WO3. However, in the solid phase, localized microwave thermal effects could reduce the interfacial area between WO3 and rGO and enhance the bonding between them. As for the unique structure and surface properties, the synthesized catalyst enhanced the light absorption, promoted the interfacial charge separation, and increased the carrier density in the photocatalytic processes. In addition, surface formation of W4+ provided a new pathway for Fe3+/Fe2+ cycling which linked the photocatalytic reaction and the Fenton process. The optimized catalyst exhibited a remarkable performance in the degradation of bisphenol A with a ∼83% removal yield via a photo-Fenton route. These microwave-induced functionalities of materials for synergistic reactions could also give a new avenue to other photoelectrocatalytic fields and solar cells.

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 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).

Construction of Defective Zinc-Cadmium-Sulfur Nanorods for Visible-Light-Driven Hydrogen Evolution Without the Use of Sacrificial Agents or Cocatalysts.

Solar-driven H2 evolution is an essential process for sustainable energy development. Currently, the greatest challenge is the development of efficient photocatalysts to drive this reaction, especially in pure water systems (without the use of a sacrificial agent). In this study, structural defects in Zn-Cd-S nanorod photocatalysts are found to increase charge separation efficiency significantly by sevenfold. Efficient H2 evolution (352.7 µmol h-1 g-1 , 100 mg of catalyst) is achieved by using this defective Zn-Cd-S nanorod photocatalyst in the absence of sacrificial agents and precious metal cocatalysts under visible-light irradiation. Thus, this cocatalyst- and sacrificial-agent-free, visible-light-responsive system shows remarkable potential as a new artificial photosynthesis route for green H2 production.

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.

A chloroplast structured photocatalyst enabled by microwave synthesis.

Photosynthesis occurs through the synergistic effects of the non-ncontinuously distributed components in the chloroplast. Inspired by nature, we mimic chloroplast and develop a generic approach to synthesize non-continuously distributed semiconductors threaded by carbon nanotubes. In the synthesis, carbon nanotubes serve as microwave antennas to produce local super-hot dots on the surface, which might induce and accelerate various organic/inorganic semiconductors assembly. With the unique nanoscale designed bionic architecture, a chloroplast structured photocatalyst with 3-dimentional dual electron transfer pathways facilitate enhanced photocatalytic performance. The as-synthesized carbon nanotubes-titanium oxide achieves a record-breaking efficiency of 86% for nitric oxide treatment under ultraviolet light irradiation. As a general strategy, a wide variety of carbon nanotubes threaded chloroplast structured nanomaterials can be synthesized and these nanomaterials could find applications in energy chemistry, environmental science and human health.

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.

A flexible CdS nanorods-carbon nanotubes/stainless steel mesh photoanode for boosted photoelectrocatalytic hydrogen evolution.

An innovative flexible reticular photoanode (CdS-nanorods/CNTs coated on stainless iron mesh) was designed for efficiently driving photoelectrocatalytic (PEC) hydrogen (H2) evolution under visible-light irradiation. Such CdS-NRs/CNTs-based flexible photoanodes exhibited a record-breaking H2 evolution rate (728 mmol h-1 g-1) among the reported CdS-based photoanodes under visible-light irradiation owing to the photoelectron transport channels (CNTs) and high separation efficiency of electrons and holes.

A graphyne-like porous carbon-rich network synthesized via alkyne metathesis.

The synthesis of graphyne has been considered challenging, especially when it comes to adopting new topologies and obtaining thinner layers. Herein, we report the synthesis and characterization of a graphyne-like porous carbon-rich network via alkyne metathesis reactions, which resulted in a sp2/sp hybridized 2D thin film structure with a layer to layer distance of 0.37 nm. This graphyne-like porous carbon-rich network is an n-type semiconductor with a low work function of 3.9 eV and a reduction potential of -0.54 V vs. SHE, which could be applied as an excellent reducing agent for metal electroless deposition. In addition, this material has a narrow pore size distribution of 2 to 4 nm, a high surface area of 675 m2 g-1 and a large pore volume of 0.795 cm3 g-1 favoring gas adsorption. It shows the selective absorption of CO2 over N2 owing to the strong affinity between CO2 and the carbon-carbon triple bond.

Porous CuO nanotubes/graphene with sandwich architecture as high-performance anodes for lithium-ion batteries.

Constructing a porous conductive framework represents a promising strategy for designing high-performance anodes for Li-ion batteries. Here, porous CuO nanotubes/graphene with hierarchical architectures were fabricated by simple annealing of copper nanowires/graphene hybrids synthesized by a microwave-assisted process. In these nanoarchitectures, the embedded porous CuO nanotubes can prevent restacking of the graphene sheets, whereas graphene can increase the electrical conductivity of CuO. Moreover, these two components constitute a sandwich-like interlaced framework that favors ion diffusion, as well as promoting better electron transport. As a result, the as-prepared nanohybrid exhibits a high specific capacity of 725 mA h g-1 and a capacity retention of ∼81% after 250 cycles, as well as outstanding rate performance in comparison to those of bare CuO or a CuO-CNT (carbon nanotubes) hybrid.

Microwave-antenna induced in situ synthesis of Cu nanowire threaded ZIF-8 with enhanced catalytic activity in H2 production.

A microwave-antenna strategy was developed for the in situ synthesis of Cu nanowire (CuNW) threaded ZIF-8. The CuNWs acted as microwave-antennas to generate surface "super hot" dots. The high temperature of "super hot" dots induced adsorption and coordination of metal ions and organic ligands, followed by in situ assembly and crystal-growth along the CuNWs. This catalyst exhibited high activity and stability in H2 production via NH3BH3 hydrolysis owing to the synergetic effect. The CuNWs supplied a rapid electron transfer channel while ZIF-8 assembled on the CuNWs offered a large capacity for adsorbing reactants and channels for rapidly transferring H(-)/H(+) ions toward Cu active sites. Other one-dimensional threaded MOFs, including CuNW threaded MOF-5 and UIO-66, or carbon nanotube threaded ZIF-8 and ZIF-67 could also be prepared using the microwave-antenna strategy.

CNTs threaded (001) exposed TiO2 with high activity in photocatalytic NO oxidation.

A microwave-ionothermal strategy was developed for in situ synthesis of CNTs threaded TiO2 single crystal with a tunable percentage of surface exposed (001) active facets. The CNTs were used as microwave antennas to create local "super hot" dots to induce Ti(3+) adsorption and hydrolysis, thereby leading to a good assembly of (001) facets exposed single crystalline TiO2 threaded by the CNTs in the presence of Hmim[BF4] ionic liquid. Due to the high percentage of the active (001) facets of single crystal TiO2 and the direct electron transfer property of the CNTs, the as-prepared CNTs-TiO2 composite showed a photocatalytic NO removal ratio of up to 76.8% under UV irradiation. In addition, with self-doped Ti(3+), the CNTs-TiO2 composite also exhibited an enhanced activity under irradiation with either solar lights or visible lights, showing good potential in practical applications for environmental remediation.

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.

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.

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.