Photocatalytic Hydrogen and Oxygen Evolution Performed by a Long-Afterglow Material.

A micron-sized long-afterglow material, Sr2MgSi2O7:Eu,Ce, was utilized to conduct the hydrogen evolution reaction and oxygen evolution reaction, two half-reactions of water splitting, in the presence of sacrificial agents under both light and dark conditions for the first time. The as-synthesized Sr2MgSi2O7:Eu,Ce exhibited higher photocatalytic activity compared to that of the referenced Sr2MgSi2O7:Eu and Sr2MgSi2O7:Ce samples. Herein, in addition to benefiting from the long photogenerated carrier lifetime of long-afterglow materials, the higher photocatalytic activity was attributed to the conjugated electronic structure between Eu and Ce ions. This structure facilitates charge and energy transfer between them, leading to an enhanced photocatalytic efficiency. This research provides a new strategy for designing efficient long-afterglow material photocatalysts through the construction of conjugated electronic structures.

Ni2P nanosheet array for high-efficiency electrohydrogenation of nitrite to ammonia at ambient conditions.

Ammonia (NH3) plays an important role in agriculture and industry. The industry-scale production mainly depends on the Haber-Bosch process suffering from issues of environment pollution and energy consumption. Electrochemical reduction can degrade nitrite (NO2-) pollutants in the environment and convert it into more valuable NH3. Here, Ni2P nanosheet array on nickel foam is proposed as a 3D electrocatalyst for high-efficiency electrohydrogenation of NO2- to NH3 under ambient reaction conditions. When tested in 0.1 M phosphate buffer saline with 200 ppm NO2-, such Ni2P/NF is able to obtain a large NH3 yield rate of 2692.2 ± 92.1 µg h-1 cm-2 (3282.9 ± 112.3 µg h-1 mgcat.-1), a high Faradic efficiency of 90.2 ± 3.0%, and selectivity of 87.0 ± 1.7% at -0.3 V versus a reversible hydrogen electrode. After 10 h of electrocatalytic reduction, the conversion rate of NO2- achieves near 100%. The catalytic mechanism is further investigated by density functional theory calculations.

Effect of bromide on molecular transformation of dissolved effluent organic matter during ozonation, UV/H2O2, UV/persulfate, and UV/chlorine treatments.

Ozonation and ultraviolet-based advanced oxidation processes (UV-AOPs) play important roles in advanced treatment of municipal wastewater for water reuse. Bromide is widely present in wastewater at different concentration levels (ranging from µg/L to mg/L). However, the effect of bromide on molecular transformation of dissolved effluent organic matter (dEfOM) in real wastewater during ozonation and UV-AOPs treatments still remains unclear. Herein, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was utilized to characterize the overall molecular transformation of dEfOM and the formation of unknown halogenated byproducts (X-BPs) in ozonation, UV/H2O2, UV/persulfate (UV/PS), and UV/chlorine (UV/Cl) processes in the presence of additional bromide. Compared with the same oxidation processes without additional bromide, the degree of dEfOM oxygenation had some extent decrement with the effect of bromide. A slightly increment of the number of unknown brominated byproducts (Br-BPs) was observed during ozonation, UV/H2O2, and UV/PS treatments in the presence of additional bromide, and the largest increment of these compounds was found in UV/Cl process. A total of 82 chlorinated byproducts (Cl-BPs) and 183 Br-BPs were detected in all oxidation processes with the effect of bromide, and the number of Br-BPs was significantly higher than that of Cl-BPs. Based on mass difference analysis, 69 pairs of possible precursors/Br-BPs were identified. In addition, the additional bromide did not remarkably increase the concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) in ozonation, UV/H2O2, and UV/PS treatments, while the production of THMs and HAAs significantly decreased by 68.06% and 54.55%, respectively, during UV/Cl treatment. The calculated cytotoxicity increased to some extent for each treatment, especially for UV/Cl treatment, and the compound with largest contribution to cytotoxicity was monobromoacetic acid. This study provides new insights into the formation and transformation of X-BPs during advanced treatment of real wastewater with the effect of bromide.

Green preparation of porous hierarchical TiO2(B)/anatase phase junction for effective photocatalytic degradation of antibiotics.

In this study, porous hierarchical bronze/anatase phase junction TiO2 assembled by ultrathin two-dimensional nanosheets was prepared by a novel, green and simple deep eutectic solvent-regulated strategy. Due to its structural features, the TiO2 sample exhibited enhanced photocatalytic activities for multiple kinds of antibiotics, including ofloxacin, ciprofloxacin and chloramphenicol.

High-efficiency nitrate electroreduction to ammonia on electrodeposited cobalt-phosphorus alloy film.

Electrocatalytic eight-electron nitrate (NO3-) reduction is a sustainable strategy to degrade NO3- and convert it into high value-added ammonia (NH3) but needs efficient catalysts with high activity and selectivity. Our study shows the use of Ti plate supported cobalt-phosphorus alloy film (Co-P/TP) as a highly active and selective electrocatalyst for ambient NO3--to-NH3 conversion. In 0.2 M Na2SO4 with 200 ppm NO3-, Co-P/TP offers an NH3 yield rate of 416.0 ± 7.2 µg h-1 cm-2 and a high faradaic efficiency of 93.6 ± 3.3% at -0.6 V and -0.3 V vs. reversible hydrogen electrode, respectively, with good durability. Noticeably, a conversion rate of 86.9% is achieved after 10 h bulk electrolysis.

Ti2O3 Nanoparticles with Ti3+ Sites toward Efficient NH3 Electrosynthesis under Ambient Conditions.

Electrocatalytic nitrogen reduction reaction (NRR) enabled by introducing Ti3+ defect sites into TiO2 through a doping strategy has recently attracted widespread attention. However, the amount of Ti3+ ions is limited due to the low concentration of dopants. Herein, we propose Ti2O3 nanoparticles as a pure Ti3+ system that performs efficiently toward NH3 electrosynthesis under ambient conditions. This work has suggested that Ti3+ ions, as the main catalytically active sites, significantly increase the NRR activity. In an acidic electrolyte, Ti2O3 achieves extraordinary performance with a high NH3 yield and a Faradaic efficiency of 26.01 µg h-1 mg-1 cat. and 9.16%, respectively, which are superior to most titanium-based NRR catalysts recently reported. Significantly, it also demonstrates a stable NH3 yield in five consecutive cycles. Theoretical calculations uncovered that the enhanced electrocatalytic activity of Ti2O3 originated from Ti3+ active sites and significantly lowered the overpotential of the potential-determining step.

Enhanced Electrochemical H2O2 Production via Two-Electron Oxygen Reduction Enabled by Surface-Derived Amorphous Oxygen-Deficient TiO2-x.

The electrochemical oxygen reduction reaction (ORR) is regarded as an attractive alternative to the anthraquinone process for sustainable and on-site hydrogen peroxide (H2O2) production. It is however hindered by low selectivity due to strong competition from the four-electron ORR and needs efficient catalysts to drive the 2e- ORR. Here, an acid oxidation strategy is proposed as an effective strategy to boost the 2e- ORR activity of metallic TiC via in-site generation of a surface amorphous oxygen-deficient TiO2-x layer. The resulting a-TiO2-x/TiC exhibits a low overpotential and high H2O2 selectivity (94.1% at 0.5 V vs reversible hydrogen electrode (RHE)), and it also demonstrates robust stability with a remarkable productivity of 7.19 mol gcat.-1 h-1 at 0.30 V vs RHE. The electrocatalytic mechanism of a-TiO2-x/TiC is further revealed by density functional theory calculations.

Honeycomb Carbon Nanofibers: A Superhydrophilic O2 -Entrapping Electrocatalyst Enables Ultrahigh Mass Activity for the Two-Electron Oxygen Reduction Reaction.

Electrocatalytic two-electron oxygen reduction has emerged as a promising alternative to the energy- and waste-intensive anthraquinone process for distributed H2 O2 production. This process, however, suffers from strong competition from the four-electron pathway leading to low H2 O2 selectivity. Herein, we report using a superhydrophilic O2 -entrapping electrocatalyst to enable superb two-electron oxygen reduction electrocatalysis. The honeycomb carbon nanofibers (HCNFs) are robust and capable of achieving a high H2 O2 selectivity of 97.3 %, much higher than that of its solid carbon nanofiber counterpart. Impressively, this catalyst achieves an ultrahigh mass activity of up to 220 A g-1 , surpassing all other catalysts for two-electron oxygen reduction reaction. The superhydrophilic porous carbon skeleton with rich oxygenated functional groups facilitates efficient electron transfer and better wetting of the catalyst by the electrolyte, and the interconnected cavities allow for more effective entrapping of the gas bubbles. The catalytic mechanism is further revealed by in situ Raman analysis and density functional theory calculations.

Photocatalytic Overall Water Splitting by SrTiO3 with Surface Oxygen Vacancies.

Strontium Titanate has a typical perovskite structure with advantages of low cost and photochemical stability. However, the wide bandgap and rapid recombination of electrons and holes limited its application in photocatalysis. In this work, a SrTiO3 material with surface oxygen vacancies was synthesized via carbon reduction under a high temperature. It was successfully applied for photocatalytic overall water splitting to produce clean hydrogen energy under visible light irradiation without any sacrificial reagent for the first time. The photocatalytic overall water splitting ability of the as-prepared SrTiO3-C950 is attributed to the surface oxygen vacancies that can make suitable energy levels for visible light response, improving the separation and transfer efficiency of photogenerated carriers.

Enhanced electrocatalytic N2-to-NH3 fixation by ZrS2 nanofibers with a sulfur vacancy.

Industrially, large-scale NH3 production is achieved by the Haber-Bosch process, which operates under harsh reaction conditions with abundant energy consumption and CO2 emission. Electrochemical N2 reduction is an eco-friendly and energy-saving method for artificial N2 to NH3 fixation under ambient reaction conditions. Herein, we demonstrate that ZrS2 nanofibers with a sulfur vacancy (ZrS2 NF-Vs) behave as an efficient electrocatalyst for ambient N2 reduction to NH3 with excellent selectivity. In 0.1 M HCl, this ZrS2 NF-Vs catalyst attains a large NH3 yield of 30.72 µg h-1 mgcat.-1 and a high faradaic efficiency of 10.33% at -0.35 V and -0.30 V vs. reversible hydrogen electrode, respectively. It also shows high electrochemical and structural stability. The density functional theory calculations reveal that the introduction of Vs facilitates the adsorption and activation of N2 molecules.

Electrochemical non-enzymatic glucose sensors: recent progress and perspectives.

The detection of glucose has important significance in clinical medicine and the food industry, especially in the diagnosis of diabetes. In recent years, electrochemical non-enzymatic glucose sensors have attracted intensive attention to detect the glucose level with great progress. In this review, we summarize a variety of non-enzymatic glucose sensor materials, including precious metals Pt, Au and their alloy metals, non-precious transition metals and their metal oxides, composites and other functional materials. Moreover, fundamental insights into the reaction mechanism and influencing factors of materials are given. Finally, this review discusses the perspectives and challenges of future developments in electrochemical non-enzymatic glucose detection.

Cu3P nanoparticle-reduced graphene oxide hybrid: an efficient electrocatalyst to realize N2-to-NH3 conversion under ambient conditions.

Industrial NH3 synthesis mainly relies on the Haber-Bosch process operated under harsh conditions. Ambient electrochemical N2 reduction offers an eco-friendly and sustainable pathway for NH3 synthesis, but its implementation depends on efficient electrocatalysts. Here, we report that a Cu3P nanoparticle-reduced graphene oxide (Cu3P-rGO) hybrid serves as an efficient electrocatalyst toward NH3 synthesis. Tested in 0.1 M HCl, Cu3P-rGO exhibits a large NH3 yield of 26.38 µg h-1 mgcat.-1 and a high faradaic efficiency of 10.11% at -0.45 V vs. the reversible hydrogen electrode, with high electrochemical stability. Theoretical calculations reveal that Cu3P can efficiently catalyze NH3 synthesis.

Grey Rutile TiO2 with Long-Term Photocatalytic Activity Synthesized Via Two-Step Calcination.

Colored titanium oxides are usually unstable in the atmosphere. Herein, a gray rutile titanium dioxide is synthesized by two-step calcination successively in a high-temperature reduction atmosphere and in a lower-temperature air atmosphere. The as-synthesized gray rutile TiO2 exhibits higher photocatalytic activity than that of white rutile TiO2 and shows high chemical stability. This is attributed to interior oxygen vacancies, which can improve the separation and transmission efficiency of the photogenerated carriers. Most notably, a formed surface passivation layer will protect the interior oxygen vacancies and provide long-term photocatalytic activity.

P-Doped graphene toward enhanced electrocatalytic N2 reduction.

Catalysts for the N2 reduction reaction (NRR) are at the heart of key alternative technology to the Haber-Bosch process for NH3 synthesis, and are expected to optimize the interplay between efficiency, activity and selectivity. Here, we report our recent finding that P-doped graphene shows superior NRR performances in aqueous media at present, with a remarkably large NH3 yield of 32.33 µg h-1 mgcat.-1 and a high faradaic efficiency of 20.82% at -0.65 V vs. reversible hydrogen electrode. The mechanism is clarified by density functional theory calculations.

The preparation of a novel iron/manganese binary oxide for the efficient removal of hexavalent chromium [Cr(vi)] from aqueous solutions.

To remove hexavalent chromium Cr(vi) efficiently, a novel Fe-Mn binary oxide adsorbent was prepared via a "two-step method" combined with a co-precipitation method and hydrothermal method. The as-prepared Fe-Mn binary oxide absorbent was characterized via transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared spectra (FTIR), thermogravimetric analysis (TGA), zeta potential, BET and X-ray photoelectron spectroscopy (XPS). The results indicated that the morphology of the adsorbent was rod-like with length of about 100 nm and width of about 50-60 nm, specific surface area was 63.297 m2 g-1, has the composition of α-Fe2O3, ß-MnO2 and MnFe2O4 and isoelectric point was observed at pH value of 4.81. The removal of Cr(vi) was chosen as a model reaction to evaluate the adsorption capacity of the Fe-Mn binary oxide adsorbent, indicating that the Fe-Mn binary oxide adsorbent showed high adsorption performance (removal rate = 99%) and excellent adsorption stability (removal rate > 90% after six rounds of adsorption). The adsorption behavior of the Fe-Mn binary oxide was better represented by the Freundlich model (adsorption isotherm) and the pseudo-second-order model (adsorption kinetic), suggesting that the adsorption process was multi-molecular layer chemical adsorption. The possible adsorption mechanism of the Fe-Mn binary oxide for the removal of Cr(vi) included the protonation process and the electrostatic attraction interactions.

Highly Selective Electrochemical Reduction of CO2 to Alcohols on an FeP Nanoarray.

Electrochemical reduction of CO2 into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO2 reduction reaction to convert CO2 into alcohols with high selectivity. In 0.5 m KHCO3 , such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE CH 3 OH ) up to 80.2 %, with a total FE CH 3 OH + C 2 H 5 OH of 94.3 % at -0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO2 toward CH3 OH owing to the synergistic effect of two adjacent Fe atoms, and the potential-determining step is the hydrogenation process of *CO.

Ti3+ self-doped TiO2-x nanowires for efficient electrocatalytic N2 reduction to NH3.

Electrochemical N2 reduction is an environmentally friendly and sustainable approach for NH3 synthesis under mild conditions, while an efficient electrocatalyst is crucial for the N2 reduction reaction (NRR). Herein, we report Ti3+ self-doped TiO2-x nanowires on Ti mesh (Ti3+-TiO2-x/TM) as an efficient non-noble-metal NRR electrocatalyst with excellent selectivity. In 0.1 M Na2SO4, the Ti3+-TiO2-x/TM achieves a high faradaic efficiency of 14.62% with a NH3 yield of 3.51 × 10-11 mol s-1 cm-2 at -0.55 V vs. the reversible hydrogen electrode. Density functional theory calculations further reveal that introducing Ti3+ decreases the reaction energy barrier and increases the number of active sites on the TiO2 surface for the NRR.

Dendritic Cu: a high-efficiency electrocatalyst for N2 fixation to NH3 under ambient conditions.

The artificial N2 fixation to NH3 is dominated by the traditional Haber-Bosch process, which consumes large amounts of energy and natural gas with low energy efficiency and large amounts of CO2 emissions. Electrochemical N2 reduction is a promising and environmentally friendly route for artificial N2-to-NH3 fixation under milder conditions. Herein, we report that dendritic Cu acts as a highly active electrocatalyst to catalyze N2 to NH3 fixation under ambient conditions. When tested in 0.1 M HCl, such an electrocatalyst achieves a high faradaic efficiency of 15.12% and a large NH3 yield rate of 25.63 µg h-1 mgcat.-1 at -0.40 V versus a reversible hydrogen electrode. Notably, this catalyst shows high electrochemical stability and excellent selectivity toward NH3 synthesis.

Greatly Improving Electrochemical N2 Reduction over TiO2 Nanoparticles by Iron Doping.

Titanium-based catalysts are needed to achieve electrocatalytic N2 reduction to NH3 with a large NH3 yield and a high Faradaic efficiency (FE). One of the cheapest and most abundant metals on earth, iron, is an effective dopant for greatly improving the nitrogen reduction reaction (NRR) performance of TiO2 nanoparticles in ambient N2 -to-NH3 conversion. In 0.5 m LiClO4 , Fe-doped TiO2 catalyst attains a high FE of 25.6 % and a large NH3 yield of 25.47 µg h-1 mgcat -1 at -0.40 V versus a reversible hydrogen electrode. This performance compares favorably to those of all previously reported titanium- and iron-based NRR electrocatalysts in aqueous media. The catalytic mechanism is further probed with theoretical calculations.

MoS2 Nanosheets Assembled on Three-Way Nitrogen-Doped Carbon Tubes for Photocatalytic Water Splitting.

In this work, a micron-sized three-way nitrogen-doped carbon tube covered with MoS2 nanosheets (TNCT@MoS2) was synthesized and applied in photocatalytic water splitting without any sacrificial agents for the first time. The micron-sized three-way nitrogen-doped carbon tube (TNCT) was facilely synthesized by the calcination of commercial sponge. The MoS2 nanosheets were assembled on the carbon tubes by a hydrothermal method. Compared with MoS2, the TNCT@MoS2 heterostructures showed higher H2 evolution rate, which was ascribed to the improved charge separation efficiency and the increased active sites afforded by the TNCT.