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Electroreduction of nitrate (NO 3 RR) to ammonia in membraneless electrolyzers is of great significance for reducing the cost and saving energy consumption. However, severe chemical crossover with side reactions makes it challenging to achieve ideal electrolysis. Herein, we propose a general strategy for efficient membraneless ammonia synthesis by screening NO 3 RR catalysts with inferior oxygen reduction activity and matching the counter electrode (CE) with good oxygen evolution activity while blocking anodic ammonia oxidation. Consequently, screening the available Co-Co system, the membraneless NO 3 - -to-NH 3 conversion performance was significantly higher than H-type cells using costly proton-exchange membranes. At 200 mA cm -2 , the full-cell voltage of the membraneless system (∼2.5 V) is 4 V lower than that of the membrane system (∼6.5 V), and the savings are 61.4 kW h (or 56.9%) per 1 kg NH 3 produced. A well-designed pulse process, inducing reversible surface reconstruction that in situ generates and restores the active Co(III) species at the working electrode and forms favorable Co 3 O 4 /CoOOH at the CE, further significantly improves NO 3 - -to-NH 3 conversion and blocks side reactions. A maximum NH 3 yield rate of 1500.9 μmol cm -2 h -1 was achieved at -0.9 V (Faraday efficiency 92.6%). This pulse-coupled membraneless strategy provides new insights into design complex electrochemical synthesis.

Electroreduction of waste nitrate to valuable ammonia offers a green solution for environmental restoration and energy storage. However, the electrochemical self-reconstruction of catalysts remains a huge challenge in terms of maintaining their stability, achieving the desired active sites, and managing metal leaching. Herein, we present an electrical pulse-driven Co surface reconstruction-coupled Co δ+ shuttle strategy for the precise in situ regulation of the Co(II)/Co(III) redox cycle on the Co-based working electrode and guiding the dissolution and redeposition of Co-based particles on the counter electrode. As result, the ammonia synthesis performance and stability are significantly promoted while cathodic hydrogen evolution and anodic ammonia oxidation in a membrane-free configuration are effectively blocked. A high rate of ammonia production of 1.4 ± 0.03 mmol cm -2 h -1 is achieved at -0.8 V in a pulsed system, and the corresponding nitrate-to-ammonia Faraday efficiency is 91.7 ± 1.0%. This work holds promise for the regulation of catalyst reactivity and selectivity by engineering in situ controllable structural and chemical transformations.

Hydrogen peroxide (H 2 O 2 ), as a critical green chemical, has received immense attention in energy and environmental fields. The ability to produce H 2 O 2 in earth-abundant water without relying on low solubility oxygen would be a sustainable and potentially economic process, applicable even to anaerobic microenvironments, such as groundwater treatment. However, the direct water to H 2 O 2 process is currently hindered by low selectivity and low production rates. Herein, we report that poly(tetrafluoroethylene) (PTFE), a commonly used inert polymer, can act as an efficient triboelectric catalyst for H 2 O 2 generation. For example, a high H 2 O 2 production rate of 24.8 mmol g cat -1 h -1 at a dosage of 0.01 g/L PTFE was achieved under the condition of pure water, ambient atmosphere, and no sacrificial agents, which exceeds the performance of state-of-the-art aqueous H 2 O 2 powder catalysts. Electron spin resonance and isotope experiments provide strong evidence that water-PTFE tribocatalysis can directly oxidize water to produce H 2 O 2 under both anaerobic and aerobic conditions, albeit with different synthetic pathways. This study demonstrates a potential strategy for green and effective tribocatalytic H 2 O 2 production that may be particularly useful toward environmental applications.

Ultrasound (US)-activated nanoagents capable of producing cytotoxic species have been promising for the treatment of deep-seated tumors; however, poor tumor uptake and insufficient generation of cytotoxic agents have largely limited their therapeutic efficacy in vivo . Herein, we report a hybrid FeCuS-lipid nanoparticle (AIBA@FeCuS-FeCO) by amphiphilic lipids-assisted emulsion of a free radical initiator (AIBA), a radical-sensitive CO donor (Fe 3 (CO) 12 ), and radical-degradable FeCuS nanodisks for US-activated synergistic therapy of deep-located orthotopic gastric tumors in living mice. Upon US irradiation, AIBA@FeCuS-FeCO could be degraded and release cytotoxic AIBA radicals, CO, Fe 2+ , and Cu 2+ , allowing us to (1) enhance tumor uptake of AIBA@FeCuS-FeCO through CO-mediated vasodilation, (2) promote hydroxyl radical production and induce tumor ferroptosis via intracellular accumulation of Fe 2+ /Cu 2+ , and (3) kill tumor cells. Moreover, the subsequent administration of disulfiram (DSF) could further chelate with the liberated Cu 2+ , yielding toxic bis( N , N -diethyl dithiocarbamato)copper(II) chelates to synergize the therapeutic effect to ablate deep-seated orthotopic gastric tumors.

About 3.93 billion tons of wastewater containing heavy metal complexes are discharged (e.g., from the electroplating industry) every year in China alone. It is challenging to appropriately treat such wastewaters. Here, a multifunctional composite nanowires BaTiO 3 @graphene was designed based on Comsol simulations and made into 3D millimeter-sphere in order to facilitate practical application. Results indicate 100% of Cu-EDTA was decomplexed in situ via piezoelectric potential by BaTiO 3 @graphene. Notably, the addition of graphene sharply increased the surface potential (from 19.8 ± 0.97 to 96.8 ± 1.48 mV) of BaTiO 3 @graphene by its flexoelectric effect then effectively promoted piezoelectric electrons to be separated and transferred, which favors the piezoelectric catalysis. Moreover, the released Cu(II) from Cu-EDTA decomplexation were recovered simultaneously via the interaction on graphene groups. This method efficiently recovered Cu(II) to avoid the consumption of massive chemical reagents and the generation of secondary hazardous solid waste containing heavy metal ions, compared with the conventional oxidative decomplexation/precipitation strategy for heavy metal complexes removal. Piezoelectric catalysis paves a new possibility for advanced oxidation in wastewater treatment.

Graphene is easily warped in the out-of-plane direction because of its high in-plane Young's modulus, and exploring the influence of wrinkled graphene on its properties is essential for the design of graphene-based materials for environmental applications. Herein, we prepared wrinkled graphene (WGN-1 and WGN-2) by thermal treatment and compared their electrochemical properties with those of flat graphene nanosheets (FGN). FGN exhibit activities that are much better than those of wrinkled graphene nanosheets (WGN), not only in the electrochemical oxidation of methylene blue (MB) but also in the electrochemical reduction of nitrobenzene (NB). Transformation ratios of MB and NB in FGN, WGN-1, and WGN-2 were 97.5, 80.1, and 57.9% and 94.6, 92.1, and 81.2%, respectively. Electrochemical impedance spectroscopy and the surface resistance of the graphene samples increased in the following order: FGN < WGN-1 < WGN-2. This suggests that the reaction charges transfer faster across the reaction interfaces and along the surface of FGN than that of WGN, and wrinkles restrict reaction charge transfer and reduce the reaction rates. This study reveals that the morphology of the graphene (flat or wrinkle) greatly affects redox reaction activities and may have important implications for the design of novel graphene-based nanostructures and for our understanding of graphene wrinkle-dependent redox reactions in environmental processes.

Responsible development of nanotechnology calls for improved understanding of how nanomaterial surface energy and reactivity affect potential toxicity. Here, we challenge the paradigm that cytotoxicity increases with nanoparticle reactivity. Higher-surface-energy {001}-faceted CdS nanorods (CdS-H) were less toxic to Saccharomyces cerevisiae than lower-energy ({101}-faceted) nanorods (CdS-L) of similar morphology, aggregate size, and charge. CdS-H adsorbed to the yeast's cell wall to a greater extent than CdS-L, which decreased endocytosis and cytotoxicity. Higher uptake of CdS-L decreased cell viability and increased endoplasmatic reticulum stress despite lower release of toxic Cd(2+) ions. Higher toxicity of CdS-L was confirmed with five different unicellular microorganisms. Overall, higher-energy nanocrystals may exhibit greater propensity to adsorb to or react with biological protective barriers and/or background constituents, which passivates their reactivity and reduces their bioavailability and cytotoxicity.

Photocatalysts with different exposed facets often exhibit different photochemical performances, but the underlying mechanisms are not fully understood. In this study, we synthesized two nanosheet-assembled bismuth oxyiodide (BiOI) microspheres with exposed (110) and (001) facets, respectively, to further investigate facet-dependent photocatalytic activity. Our experimental results showed that the BiOI microspheres with exposed (110) facets exhibited much greater catalytic activity than the BiOI microspheres with exposed (001) facets in the degradation of bisphenol A under visible light irradiation. Density functional theory calculation revealed that the (110) facets can adsorb a greater amount of O2 and, thus, form more O2(•-) and (•)OH radicals than the (001) facets. The electron spin resonance spectroscopy and radical scavenging experiments verified that the BiOI microspheres with exposed (110) facets could produce a greater amount of O2(•-) radicals than the BiOI microspheres with exposed (001) facets, and more importantly, between the two BiOI products, only the BiOI microspheres with exposed (110) facets could generate (•)OH radicals directly. The facet-dependent radical formation mechanisms were previously unidentified. The findings of this study may have important implications for the understanding of the facet-dependent photochemical performance of photocatalysts and the design of novel catalytic materials with inorganic nanostructures.

Electro-Fenton is a promising advanced oxidation process for water treatment consisting a series redox reactions. Here, we design and examine an electrochemical filter for sequential electro-Fenton reactions to optimize the treatment process. The carbon nanotube (CNT) membrane stack (thickness ∼ 200 μm) used here consisted of 1) a CNT network cathode for O2 reduction to H2O2, 2) a CNT-COOFe(2+) cathode to chemical reduction H2O2 to (•)OH and HO(-) and to regenerate Fe(2+) in situ, 3) a porous PVDF or PTFE insulating separator, and 4) a CNT filter anode for remaining intermediate oxidation intermediates. The sequential electro-Fenton was compared to individual electrochemical and Fenton process using oxalate, a persistent organic, as a target molecule. Synergism is observed during the sequential electro-Fenton process. For example, when [DO]in = 38 ± 1 mg L(-1), J = 1.6 mL min(-1), neutral pH, and Ecell = 2.89 V, the sequential electro-Fenton oxidation rate was 206.8 ± 6.3 mgC m(-2) h(-1), which is 4-fold greater than the sum of the individual electrochemistry (16.4 ± 3.2 mgC m(-2) h(-1)) and Fenton (33.3 ± 1.3 mgC m(-2) h(-1)) reaction fluxes, and the energy consumption was 45.8 kWh kgTOC(-1). The sequential electro-Fenton was also challenged with the refractory trifluoroacetic acid (TFA) and trichloroacetic acid (TCA), and they can be transferred at a removal rate of 11.3 ± 1.2 and 21.8 ± 1.9 mmol m(-2) h(-1), respectively, with different transformation mechanisms.

Three-dimensional porous electrodes often suffer from diffusional mass-transfer limitations that may be overcome by having the target solution flow through the electrode. Here, we examine the reactive depth and performance of an electrochemical carbon nanotube (CNT) network toward phenol removal and oxidation in the batch and flow configurations where mass transport into the CNT network is predominantly via diffusion and convection, respectively. Scanning electron microscopy depth profile imaging of phenol electropolymerization is used as a direct probe of the reactive depth. In the batch case, electropolymerization is observed to be greatest at the network surface nearest the cathode and decreases linearly to near zero at a depth of 25 μm. In stark contrast, electropolymerization is observed to be independent of the depth in the flow configuration. In agreement with the depth profile results, phenol removal is increased up to 10-fold, the current efficiency is increased by at least 2-fold, and susceptibility toward passivation is reduced in the flow versus batch configuration. Thus, the enhanced electrochemical performance in the flow configuration is partially due to the convective "activation" of the internal CNT network electron-transfer sites that are diffusion-inaccessible.

Electrochemical filtration with anodic carbon nanotube (CNT) networks is reported to be effective for chemical and microbiological water treatment. Here, we investigate how CNT doping affects the electrochemical filtration performance toward the remediation of aromatic wastewaters. Purified and well-characterized undoped (C-CNT), boron-doped (B-CNT), and nitrogen-doped (N-CNT) anodic carbon nanotube networks are challenged with aqueous phenol in a sodium sulfate electrolyte. Steady-state current and effluent total organic carbon (TOC) measurements are utilized to evaluate the oxidative performance as a function of voltage and electrolysis time. In terms of steady-state TOC removal, at an applied voltage of 3 V all three anodic CNT networks are able to remove approximately 7 to 8 mgC L(-1) of the influent TOC within the ~1 s liquid residence time of the electrochemical filter. The anodic CNT networks are partially passivated over the 5 h electrolysis time with the B-CNT network displaying the least passivation. The extent of passivation was observed to be inversely correlated to the CNT work function. SEM, XPS, and TGA of the electrolyzed CNT networks are used to identify the two primary passivation mechanisms of electrochemical phenols polymerization and electrochemical electrolyte precipitation. In agreement with chronoamperometry results, the B-CNT network has the lowest extent of passivating polymer and precipitate formation. The precipitant is determined to likely be sodium persulfate or carbonate and is removed with a simple acidic water wash. The polymer is determined to likely be polyphenylene oxide and is partially removed with the wash. All three anodic CNT networks display potential for energy efficient electrochemical filtration of aromatic wastewaters and the B-CNT are determined to be the most resistant to passivation., (© 2012 American Chemical Society)

An electrochemical carbon nanotube filter has been reported to be effective for the removal and electrooxidation of aqueous chemicals and microorganisms. Here, we investigate how carbon nanotube (CNT) chemical surface treatments including calcination to remove amorphous carbon, acid treatment to remove internal residual metal oxide, formation of surficial oxy-functional groups, and addition of Sb-doped SnO(2) particles affect the electrooxidative filter performance. The various CNT samples are characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) and electrochemically evaluated by cyclic voltammetry, open circuit potential versus time analysis, and electrochemical impedance spectroscopy. Voltammetry results indicate that the near CNT surface pH is at least two units lower than the bulk pH. The electrooxidative performance of the various CNT samples is evaluated with 1 mM of methyl orange (MO) in 100 mM sodium sulfate at a flow rate of 1.5 mL min(-1). At both 2 and 3 V, the efficacy of electrochemical filtration is observed to be function of CNT surface chemistry. The samples with the greatest electrooxidation were the calcinated then HCl-treated CNTs, i.e., the CNTs with the most surficial sp(2)-bonded carbon, and the Sb-SnO(2)-coated CNTs, i.e., the CNTs with the most electrocatalytic surface area. At 3 V applied voltage, these CNT samples are able to oxidize 95% of the influent MO within the liquid residence time of <1.2 s. The broader applicability of electrochemical filtration is evaluated by challenging the C-CNT-HCl and C-CNT-HNO(3) networks with various organics including methylene blue, phenol, methanol, and formaldehyde. At 3 V applied voltage, both CNTs are able to degrade a fraction of all the organics with the extent organic degradation dependent on both CNT and organic properties. The C-CNT-HCl network generally had the better oxidative performance than the C-CNT-HNO(3) network with an exception being the positively charged methylene blue. The extent of MO degradation, steady-state current, anode potential, effluent pH, and back pressure are also measured as a function of applied voltage (1-3 V) and CNT surface chemistry. Mass spectrometry of electrochemical CNT filter effluent at 2 and 3 V is utilized to evaluate plausible electrooxidation products. Energy consumption as compared to state-of-the-art electrodes and strategies to tailor the CNT surface for a specific target molecule are discussed.

This paper describes the fabrication of two different 3D mesoporous TiO2 microspheres via one-step solvothermal process without templates using different titanium sources. The resulting materials were characterized by XRD, FESEM, TEM, and nitrogen adsorption techniques. Their photodegradation of bisphenol A [2,2-bis(4-hydroxyphenyl)propane, BPA] in aqueous suspension was investigated under UV irradiation. The experimental results revealed that the photocatalytic effect of the two 3D mesoporous TiO2 microspheres was superior to the commercial P25 TiO2, and as-prepared samples as catalysts demonstrated that the smaller pore size it is, the higher the effective degradation for BPA is. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of BPA by HPLC-MS and HPLC-MS-MS. Five main intermediates were formed during photocatalytic degradation, and their evolution was discussed. On the basis of the evidence of oxidative intermediate formation, a detailed degradation pathway of BPA degradation by two mesoporous TiO2 microspheres photocatalysts are proposed.

Nanostructured TiO2 with different hierarchical morphologies were synthesized via a warmly hydrothermal route. The properties of the products were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, N2 adsorption, UV-vis spectroscopy, etc. Two of the products, TiO2 1D nanorods (one-dimensional rutile TiO2 nanorods) and TiO2 3D0D microspheres (three-dimensional anatase TiO2 nanoparticle-assembled microspheres) exhibited superior photocatalytic effects on phenol degradation under UV illumination, compared with TiO2 3D1D microspheres (three-dimensional rutile TiO2 nanorods-assembled microspheres). Moreover, TiO2 3D0D was superior to TiO2 1D, as indicated by a 30% higher mineralization of dissolved phenol. Dihydroxybenze, 4,4'-dihydroxybiphenyl, benzoquinone, maleic anhydride, etc. were identified as the degradation intermediates. The excellent catalytic effect was attributed to the structural features of TiO2 1D nanorods and TiO2 3D0D microspheres, that is, a larger amount of surface active sites and a higher band gap energy resulted in more efficient decomposition of organic contaminants.