High-efficiency electrocatalytic nitrite-to-ammonia conversion on molybdenum doped cobalt oxide nanoarray at ambient conditions.

Electrochemical conversion of nitrite (NO2-) contaminant to green ammonia (NH3) is a promising approach to achieve the nitrogen cycle. The slow kinetics of the complex multi-reaction process remains a serious issue, and there is still a need to design highly effective and selective catalysts. Herein, we report that molybdenum doped cobalt oxide nanoarray on titanium mesh (Mo-Co3O4/TM) acts as a catalyst to facilitate electroreduction of NO2- to NH3. Such a catalyst delivers an extremely high Faradaic efficiency of 96.9 % and a corresponding NH3 yield of 651.5 µmol h-1 cm-2 at -0.5 V with strong stability. Density functional theory calculations reveal that the introduction of Mo can induce the redistribution of electrons around Co atoms and further strengthen the adsorption of NO2-, which is the key to facilitating the catalytic performance. Furthermore, the assembled battery based on Mo-Co3O4/TM suggests its practical application value.

3D cauliflower-like Ni foam: a high-efficiency electrocatalyst for ammonia production via nitrite reduction.

A 3D cauliflower-like Ni foam on titanium plate (Ni foam/TP) shows high electrocatalytic performance for ambient ammonia (NH3) synthesis via nitrite (NO2-) reduction. In 0.1 M phosphate-buffered saline solution with 0.1 M NO2-, such Ni foam/TP attains a high NH3 Faradaic efficiency (FE) of 95.9% and a large NH3 yield of 742.7 µmol h-1 cm-2 at -0.8 V. Its Zn-NO2- battery offers a high power density of 6.2 mW cm-2 and an NH3 FE of 90.1%.

Bismuth-Decorated Honeycomb-like Carbon Nanofibers: An Active Electrocatalyst for the Construction of a Sensitive Nitrite Sensor.

The existence of carcinogenic nitrites in food and the natural environment has attracted much attention. Therefore, it is still urgent and necessary to develop nitrite sensors with higher sensitivity and selectivity and expand their applications in daily life to protect human health and environmental safety. Herein, one-dimensional honeycomb-like carbon nanofibers (HCNFs) were synthesized with electrospun technology, and their specific structure enabled controlled growth and highly dispersed bismuth nanoparticles (Bi NPs) on their surface, which endowed the obtained Bi/HCNFs with excellent electrocatalytic activity towards nitrite oxidation. By modifying Bi/HCNFs on the screen-printed electrode, the constructed Bi/HCNFs electrode (Bi/HCNFs-SPE) can be used for nitrite detection in one drop of solution, and exhibits higher sensitivity (1269.9 µA mM-1 cm-2) in a wide range of 0.1~800 µM with a lower detection limit (19 nM). Impressively, the Bi/HCNFs-SPE has been successfully used for nitrite detection in food and environment samples, and the satisfactory properties and recovery indicate its feasibility for further practical applications.

High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co3O4 Nanoarray Catalyst with Cobalt Vacancies.

Electrocatalytic nitrate reduction reaction (NO3RR) affords a bifunctional character in the carbon-free ammonia synthesis and remission of nitrate pollution in water. Here, we fabricated the Co3O4 nanosheet array with cobalt vacancies on carbon cloth (vCo-Co3O4/CC) by in situ etching aluminum-doped Co3O4/CC, which exhibits an excellent Faradaic efficiency of 97.2% and a large NH3 yield as high as 517.5 µmol h-1 cm-2, better than the pristine Co3O4/CC. Theoretical calculative results imply that the cobalt vacancies can tune the local electronic environment around Co sites of Co3O4, increasing the charge and reducing the electron cloud density of Co sites, which is thus conducive to adsorption of NO3- on Co sites for greatly enhanced nitrate reduction. Furthermore, the vCo-Co3O4 (311) facet presents excellent NO3RR activity with a low energy barrier of about 0.63 eV on a potential-determining step, which is much smaller than pristine Co3O4 (1.3 eV).

Dual-readout performance of Eu3+-doped nanoceria as a phosphatase mimic for degradation and detection of organophosphate.

Eu3+-Doped nanoceria (Eu:CeO2) with self-integrated catalytic and luminescence sensing functions was synthesized by a simple and gentle one-pot method to build a dual-readout nanozyme platform for organophosphate compound (OPC) sensing in this work. The catalytic degradation of the model substrate of OPC, p-nitrophenyl phosphate (p-NPP), by as-prepared Eu:CeO2 can be completed in 2 min with little influence of temperature and pH values, highlighting the advantages of Eu:CeO2 as an artificial enzyme for dephosphorylation. Most importantly, the characteristic red emission of Eu3+ (592 nm) from Eu:CeO2 can be quenched by p-NPP, accompanied by a color change from colorless to yellow. Based on this, linear ranges of 4-50 µM with a detection limit of 3.3 µM and 1-20 µM with a detection limit of 0.6 µM for p-NPP were obtained by colorimetric and fluorescence methods, respectively. Furthermore, the fluorescence strategy was effectively applied to the determination of ethyl para-nitrophenyl (EPN), one of the most commonly used pesticides, with a detection limit of 5.86 µM. The proposed strategy was also successfully applied to the assay of p-NPP and EPN in real water samples, showing great application prospects in detecting OPC in the environment.

Greatly Facilitated Two-Electron Electroreduction of Oxygen into Hydrogen Peroxide over TiO2 by Mn Doping.

Ambient electrochemical oxygen reduction into valuable hydrogen peroxide (H2O2) via a selective two-electron (2e-) pathway is regarded as a sustainable alternative to the industrial anthraquinone process, but it requires advanced electrocatalysts with high activity and selectivity. In this study, we report that Mn-doped TiO2 behaves as an efficient electrocatalyst toward highly selective H2O2 synthesis. This catalyst exhibits markedly enhanced 2e- oxygen reduction reaction performance with a low onset potential of 0.78 V and a high H2O2 selectivity of 92.7%, much superior to the pristine TiO2 (0.64 V, 62.2%). Additionally, it demonstrates a much improved H2O2 yield of up to 205 ppm h-1 with good stability during bulk electrolysis in an H-cell device. The significantly boosted catalytic performance is ascribed to the lattice distortion of Mn-doped TiO2 with a large amount of oxygen vacancies and Ti3+. Density functional theory calculations reveal that Mn dopant improves the electrical conductivity and reduces ΔG*OOH of pristine TiO2, thus giving rise to a highly efficient H2O2 production process.

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.

In Situ Derived Bi Nanoparticles Confined in Carbon Rods as an Efficient Electrocatalyst for Ambient N2 Reduction to NH3.

Electrocatalytic N2 reduction is deemed as a prospective strategy toward low-carbon and environmentally friendly NH3 production under mild conditions, but its further application is still plagued by low NH3 yield and poor faradaic efficiency (FE). Thus, electrocatalysts endowing with high activity and satisfying selectivity are highly needed. Herein, Bi nanoparticles in situ confined in carbon rods (Bi NPs@CRs) are reported, which are fabricated via thermal annealing of a Bi-MOF precursor as a high-efficiency electrocatalyst for artificial NH3 synthesis with favorable selectivity. Such an electrocatalyst conducted in 0.1 M HCl achieves a high FE of 11.50% and a large NH3 yield of 20.80 µg h-1 mg-1cat. at -0.55 and -0.60 V versus reversible hydrogen electrode, respectively, which also possesses high electrochemical durability.

Silicon nanoparticles-based ratiometric fluorescence platform: Real-time visual sensing to ciprofloxacin and Cu2.

In this work, a silicon nanoparticles (Si NPs)-based ratiometric fluorescence sensing platform was conveniently fabricated by simply mixing fluorescent Si NPs as co-ligands and reference signal with lanthanide metal ion Eu3+ as response signal. The introduction of ciprofloxacin (CIP) remarkably turned on the characteristic fluorescence of Eu3+ at 590 nm and 619 nm through the "antenna effect". At the same time, the blue emission of Si NPs at 445 nm kept comparatively stable. A good linear relationship between the ratio fluorescence intensity and CIP concentration in the range of 0.211-132.4 µM with a limit of detection (LOD) of 89 nM was obtained. In the presence of Cu2+, the fluorescence emission of Eu3+ was sharply turned off because of the stronger coordination ability of Cu2+ with CIP, which guaranteed the sequential detection of Cu2+. Meanwhile, the distinct fluorescent color change from bright blue to red, then back to blue, enabled naked-eye visual detection of CIP and Cu2+ in the solution phase and on paper-based test strip, and was successfully applied to determine the levels of CIP in complicated food samples with high sensitivity.

Organic carbon dot coating for superhydrophobic aluminum alloy surfaces.

A novel fluorine-free and silicon-free superhydrophobic aluminum alloy (treated-Al) is fabricated by chemical etching using hydrochloric acid and hydrogen peroxide and modified with an organic carbon dot (OCD) coating. The water contact angle (CA) of the treated-Al surface increases with the OCD concentration. When etched aluminum (etched-Al) is modified with 0.5 mg/ml OCDs, a CA of 161.4° is achieved, which indicates good nonwettability. SEM results verify that porous microstructures with cavities are uniformly distributed on the surface of etched-Al, in contrast to the bare aluminum alloy, which forms a primary rough structure. After treatment with 0.5 mg/ml OCDs, a nanoparticle coating is dispersed on the rough structures of treated-Al-0.5, which can trap air and make a water droplet essentially rest on a layer of air. The treated-Al-0.5 material has good self-cleaning properties and can sweep away contaminants at both 20 and 0°C. The Ecorr and Icorr of treated-Al-0.5 are - 0.56 V and 2.82 × 10-6 A/cm2, respectively, which shows good anticorrosion performance.

Simulation and Experimental Study on Doubled-Input Capacitively Coupled Contactless Conductivity Detection of Capillary Electrophoresis.

In this contribution, we optimize the structure of double-input capacitively coupled contactless conductivity detector (DIC4D) that proposed before by our group and successfully applied it in the capillary electrophoresis of inorganic ion analysis. Furthermore, we present the detail theoretical analysis and simulation to exploring the working mechanism of DIC4D. Compared with C4D, under identical experimental conditions and by using the same current-to-voltage converter, both the theoretical and experimental results suggest that the effectiveness and feasibility of DIC4D. The improved DIC4D diminished the baseline drift effects in C4D, provides lower noise, higher sensitivity and notably stable baseline. The LODs of DIC4D are 1.0 µM for K+ and 1.5 µM for Li+ (S/N = 3). DIC4D provides a better linear relationship (R = 0.997 and 0.998 for K+ and Li+, respectively) with the range of 2.0 µM ~ 2.5 mM.

Bi nanodendrites for efficient electrocatalytic N2 fixation to NH3 under ambient conditions.

Electrochemical N2 reduction has emerged as a sustainable and eco-friendly route for the artificial synthesis of NH3 under ambient conditions, but active electrocatalysts are needed to drive the N2 reduction reaction (NRR). Here, Bi nanodendrites are reported as an efficient NRR electrocatalyst for N2 to NH3 conversion with excellent selectivity. In 0.1 M HCl, this catalyst achieves a large NH3 yield of 25.86 µg h-1 mg-1cat. and a high faradaic efficiency of 10.8% at -0.60 V and -0.55 V versus a reversible hydrogen electrode, respectively, with high electrochemical durability.

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 synthesis of highly active carbon dot-coated gold nanoparticles via the room-temperature in situ carbonization of organic ligands for 4-nitrophenol reduction.

Due to the serious pollution issue caused by 4-nitrophenol (4-NP), it is of great importance to design effective catalysts for its reduction. Here, a novel and simple strategy was developed for the synthesis of carbon dot-decorated gold nanoparticles (AuNPs/CDs) via the in situ carbonization of organic ligands on AuNPs at room temperature. The enhanced adsorption of 4-NP on CDs via π-π stacking interactions provided a high concentration of 4-NP near AuNPs, leading to a more effective reduction of 4-NP.

Unusual electrochemical N2 reduction activity in an earth-abundant iron catalyst via phosphorous modulation.

Fe-enabled high-performance ambient electrochemical N2 reduction still remains a big challenge. Here, we report the unusual role of phosphorous in modulating the electrochemical N2 reduction activity of an Fe catalyst. An FeP2 nanoparticle-reduced graphene oxide hybrid (FeP2-rGO) attains a large NH3 yield of 35.26 µg h-1 mgcat.-1 (7.06 µg h-1 cm-2) and a high faradaic efficiency of 21.99% at -0.40 V vs. reversible hydrogen electrode in 0.5 M LiClO4, outperforming the FeP-rGO hybrid (17.13 µg h-1 mgcat.-1; 8.57%). Theoretical calculations reveal that FeP2 possesses decreased catalytic activity for the hydrogen evolution reaction, higher N2 adsorption energy, and a larger number of active sites than FeP.

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.

Construction of hydrophobic interface on natural biomaterials for higher efficient and reversible radioactive iodine adsorption in water.

For the pollution of radioactive materials, it is of great importance to develop efficient adsorbents for radioactive iodine adsorption in aqueous solution. In this work, a simple and green strategy was developed to construct hydrophobic surface on natural cotton fibers (n-CF) based on organic-soluble carbon dots (OCDs) for the first time. The results demonstrated the successful constructed hydrophobic n-CF@OCDs expressed excellent stability and selectivity for iodine (I2) adsorption in water. The maximum adsorption capacity for I2 on n-CF@OCDs is calculated to be 190.1 mg g-1, which is about 6.8 times higher than that of n-CF (28.1 mg g-1), this highly I2 adsorption efficiency should be attributed to the hydrophobic properties of adsorbent. The adsorption mechanism was also discussed in this work. In addition, the adsorbed I2 could be desorbed easily with a simple reductive process at ambient conditions, which can lead to not only the restore of I2 but also the recycling of adsorbent, illustrating their good practicability. Furthermore, this universal strategy can also be used for construction of hydrophobic surface on various natural biomaterials, demonstrating its potential application in constructing of hydrophobic surface and used for the adsorption and removal of nonpolar pollutions or radioactive waste in aqueous solutions.

Construction of a luminescent sensor based on a lanthanide complex for the highly efficient detection of methyl parathion.

A highly sensitive and selective luminescent sensor for the detection of methyl parathion (MP) pesticide was described in this study. The target molecule HL was synthesized by modifying the structure of 4-hydroxybenzlidene imidazolinone (HBI) with nitrogen-containing heterocyclic 1,10-phenanthroline. In the presence of Eu3+, a HL-Eu3+ complex was formed which could emit strong red fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from HL to Eu3+. Addition of MP into the strongly fluorescent solution of HL-Eu3+ induced quenching of the complex's fluorescence, and this quenching behavior occurred because of the competition coordination of MP and HL for Eu3+. A calibration curve was developed that related the extent of fluorescence quenching to MP concentration, making the HL-Eu3+ system a sensitive and selective fluorescent sensor for MP. Under the experimental conditions, the detection limit for MP was down to 95 nM based on LOD = 3σ/S. Moreover, the fluorescence assay developed here allowed the detection of MP in two different types of real samples including pond water and pear juice, and satisfactory results demonstrate that this fluorescent sensor based on HL-Eu3+ has potential application in environment and food analysis.

Nanostructured Bromide-Derived Ag Film: An Efficient Electrocatalyst for N2 Reduction to NH3 under Ambient Conditions.

Electrochemical reduction has been regarded as a sustainable strategy to tackle energy-intensive operations by the Haber-Bosch process achieving catalytic conversion of N2 to NH3 under mild conditions. However, the challenge of N2 electroconversion emphasizes the requirement of efficient electrocatalysts. In this paper, we report the development of porous bromide-derived Ag film (BD-Ag/AF) as an efficient electrocatalyst for N2 reduction reaction. During electrochemical test, Br- anions are released and adsorbed onto the surfaces of the electrode, suppressing hydrogen evolution reaction. Such BD-Ag/AF shows a high Faradaic efficiency of 7.36% at -0.6 V vs reversible hydrogen electrode in 0.1 M Na2SO4, which is higher than that (0.38%) of porous Ag film without Br- anions. Moreover, it exhibits excellent long-term electrochemical durability.

Enabling Effective Electrocatalytic N2 Conversion to NH3 by the TiO2 Nanosheets Array under Ambient Conditions.

NH3 serves as an attractive hydrogen storage medium and a renewable energy sector for a sustainable future. Electrochemical reduction is a feasible ambient reaction to convert N2 to NH3, while it needs efficient electrocatalysts for the N2 reduction reaction (NRR) to meet the challenge associated with N2 activation. In this Letter, we report on our recent experimental finding that the TiO2 nanosheets array on the Ti plate (TiO2/Ti) is effective for electrochemical N2 conversion to NH3 at ambient conditions. When tested in 0.1 M Na2SO4, such TiO2/Ti attains a high NH3 yield of 9.16 × 10-11 mol s-1·cm-2 with corresponding Faradaic efficiency of 2.50% at -0.7 V vs reversible hydrogen electrode, outperforming most reported aqueous-based NRR electrocatalysts. It also shows excellent selectivity for NH3 formation with high electrochemical stability. The superior NRR activity is due to the enhanced adsorption and activation of N2 by oxygen vacancies in situ generated during electrochemical tests.