Spatially Separated Cu/Ru on Ordered Mesoporous Carbon for Superior Ammonia Electrosynthesis from Nitrate over a Wide Potential Window.

Nitrate (NO3-) in wastewater poses a serious threat to human health and the ecological environment. The electrocatalytic NO3- reduction to ammonia (NH3) reaction (NO3-RR) emerges as a promising carbon-free energy route for enabling NO3- removal and sustainable NH3 synthesis. However, it remains a challenge to achieve high Faraday efficiencies at a wide potential window due to the complex multiple-electron reduction process. Herein, spatially separated dual-metal tandem electrocatalysts made of a nitrogen-doped ordered mesoporous carbon support with ultrasmall and high-content Cu nanoparticles encapsulated inside and large and low-content Ru nanoparticles dispersed on the external surface (denoted as Ru/Cu@NOMC) are designed. In electrocatalytic NO3-RR, the Cu sites can quickly convert NO3- to adsorbed NO2- (*NO2-), while the Ru sites can efficiently produce active hydrogen (*H) to enhance the kinetics of converting *NO2- to NH3 on the Cu sites. Due to the synergistic effect between the Cu and Ru sites, Ru/Cu@NOMC exhibits a maximum NH3 Faradaic efficiency (FENH3) of approximately 100% at -0.1 V vs reversible hydrogen electrode (RHE) and a high NH3 yield rate of 1267 mmol gcat-1 h-1 at -0.5 V vs RHE. Finite element method (FEM) simulation and electrochemical in situ Raman spectroscopy revealed that the mesoporous framework can enhance the intermediate concentration due to the in situ confinement effect. Thanks to the Cu-Ru synergistic effect and the mesopore confinement effect, a wide potential window of approximately 500 mV for FENH3 over 90% and a superior stability for NH3 production over 156 h can be achieved on the Ru/Cu@NOMC catalyst.

Copper-Based Electrocatalysts for Nitrate Reduction to Ammonia.

Ammonia (NH3) is a highly important industrial chemical used as fuel and fertilizer. The industrial synthesis of NH3 relies heavily on the Haber-Bosch route, which accounts for roughly 1.2% of global annual CO2 emissions. As an alternative route, the electrosynthesis of NH3 from nitrate anion (NO3-) reduction (NO3-RR) has drawn increasing attention, since NO3-RR from wastewater to produce NH3 can not only recycle waste into treasure but also alleviate the adverse effects of excessive NO3- contamination in the environment. This review presents contemporary views on the state of the art in electrocatalytic NO3- reduction over Cu-based nanostructured materials, discusses the merits of electrocatalytic performance, and summarizes current advances in the exploration of this technology using different strategies for nanostructured-material modification. The electrocatalytic mechanism of nitrate reduction is also reviewed here, especially with regard to copper-based catalysts.

Insight into the Fe-Ni/biochar composite supported three-dimensional electro-Fenton removal of electronic industry wastewater.

For the efficient removal of the bio-refractory organic pollutants in the electronic industry wastewater, the Ni-Fe (oxides) modified three-dimension (3D) particle electrode was applied in electro-Fenton system (3D/EF), where iron ions were released from anode and deposited onto algal biochar (ABC) to prepare composite catalyst during reaction process. Firstly, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) analysis were applied to confirm successful fabrication of the 3D particle electrode materials. Secondly, COD removal efficiency could reach about 80%, which was about 20% higher than that in 2D/EF system, under the optimized conditions as 2.0 g/L of Ni-ABC particle electrodes, initial pH of 3, 100 mL/min of aeration intensity and 20 mA/cm2 of applied current density. Thirdly, characterized using three-dimensional fluorescence spectroscopy and GC-MS analysis, it seemed that most of the macromolecular substances could be degraded, whereas mono-2-ethylhexyl phthalate (MEHP) was identified as the most abundant and representative compound. Finally, possible degradation pathway of MEHP in 3D/EF system was proposed including dealkylation, cleavage of C-O bond, and demethylation. Therefore, this study provides a new strategy in designing EF system employing bimetal doped biochar composite for an efficient elimination of organic pollutants within electronic industry wastewater.

Promoting selective water decontamination via boosting activation of periodate by nanostructured Ru-supported Co3O4 catalysts.

The superior catalytic efficiency of ruthenium (Ru)-based nanocomposites in advanced oxidation processes for water decontamination has attracted accumulating attention worldwide. However, rather limited knowledge is currently available regarding their roles in activating periodate (PI), an emerging oxidant with versatile environmental applications. This study firstly delineated that Ru-supported Co3O4 (Ru/Co3O4), a typical Ru-based nanomaterial, can efficiently accomplish PI activation to eliminate multiple organic micropollutants and inactivate different pathogenic bacteria. Almost all eight micropollutants can be completely removed within 2 min of Ru/Co3O4-PI oxidation except sulfamethoxazole (SMX), which was degraded ∼70 % at 2 min with 100 % mineralization after 10 min. The excellent catalytic performance was independent of PI dosages, initial pH, and coexisting water constituents, demonstrating its prominent capability as a selective oxidation strategy. Diverse lines of evidence indicated the dominant role of single oxygen in the Ru/Co3O4-PI system, which triggered the generation of five transformation products of SMX with reduced environmental risks. Concurrently, PI was stoichiometrically converted to the eco-friendly IO3-. Additionally, Ru/Co3O4-PI system achieved 6-log inactivation of different pathogenic bacteria within 1 min, implying the feasibility of rapid water disinfection. Overall, this work demonstrated the excellent promise of Ru-based composites in PI activation for highly efficient and selective water decontamination.

Ampere-level current density ammonia electrochemical synthesis using CuCo nanosheets simulating nitrite reductase bifunctional nature.

The development of electrocatalysts capable of efficient reduction of nitrate (NO3-) to ammonia (NH3) is drawing increasing interest for the sake of low carbon emission and environmental protection. Herein, we present a CuCo bimetallic catalyst able to imitate the bifunctional nature of copper-type nitrite reductase, which could easily remove NO2- via the collaboration of two active centers. Indeed, Co acts as an electron/proton donating center, while Cu facilitates NOx- adsorption/association. The bio-inspired CuCo nanosheet electrocatalyst delivers a 100 ± 1% Faradaic efficiency at an ampere-level current density of 1035 mA cm-2 at -0.2 V vs. Reversible Hydrogen Electrode. The NH3 production rate reaches a high activity of 4.8 mmol cm-2 h-1 (960 mmol gcat-1 h-1). A mechanistic study, using electrochemical in situ Fourier transform infrared spectroscopy and shell-isolated nanoparticle enhanced Raman spectroscopy, reveals a strong synergy between Cu and Co, with Co sites promoting the hydrogenation of NO3- to NH3 via adsorbed *H species. The well-modulated coverage of adsorbed *H and *NO3 led simultaneously to high NH3 selectivity and yield.

High activity of step sites on Pd nanocatalysts in electrocatalytic dechlorination.

The role of step sites on nanocatalysts in the electrocatalytic dechlorination reaction (ECDR) was studied using 3 Pd nanocatalysts with different densities of step sites, which decreased in the order of: tetrahexahedral Pd{310} nanocrystals (THH Pd{310} NCs) > commercial Pd nanoparticles (Pd black) > cubic Pd{100} NCs. The two well-defined Pd NCs served as model catalysts and were prepared through the electrochemical square-wave potential (SWP) method. The toxic herbicide alachlor was first employed in this study as an objective probe to determine the dechlorination performance, which was quantified by the alachlor removal (Rala), the current efficiency (CEala), and the dechlorination selectivity (Sdes). The experimental results demonstrated that the THH Pd{310} NCs with abundant step sites exhibited much higher electrocatalytic performance compared to the cubic Pd{100} NCs with terrace sites. The combination of cyclic voltammetry studies, electrochemical in situ FTIR analysis, and density functional theory (DFT) calculations revealed that the adsorbed CO bond and generated on the step sites could lower the C-Cl bond splitting barrier, leading to a high ECDR efficiency. Other chlorinated organics with an activated carbon atom were also investigated, which revealed that the superiority of the step sites toward Cl-C bond breaking was particular to the compounds with CO bonds. This study provides a deep understanding of high actvitiy of step sites on Pd NCs in EHDC and a strategy to improve this important environmental electrocatalysis process.

Efficient Dechlorination of α-Halocarbonyl and α-Haloallyl Pollutants by Electroreduction on Bismuth.

The electrocatalytic activity of bismuth considered as a low-cost and green electrode material was studied in reductive dechlorination processes. Cyclic voltammetry analyses showed that the Bi electrode exhibited a high catalytic activity to reduce alachlor, a chlorinated herbicide, in the aqueous medium at different pH values. Bulk electrolyses were performed at different potentials and pH values. Alachlor was reduced in deschloroalachlor, its dechlorinated derivative, with a high selectivity (96%) and a current efficiency of 48%. The reductive dechlorination of other chlorinated compounds with an activated carbon atom was then studied, showing that the bismuth electrode catalyzed the electroreduction of chloroacetamides, α-halocarbonyl, and α-haloallyl pollutants. Cyclic voltammetry experiments allowed us to propose a mechanism explaining the high catalytic activity of bismuth to reduce these families of compounds.

Sorption behavior of tetracyclines on suspended organic matters originating from swine wastewater.

Tetracyclines (TCs) discharged from livestock wastewater have aroused public concerns due to their pharmacological threats to ecosystems and human health. As an important medium in the wastewater, suspended organic matters (SOMs) play vital roles in antibiotics transport and degradation. However, limited information has been reported in the relevant literature. This study investigated TCs sorption behavior on SOM, withdrawn from swine wastewater. High TCs sorption capacities were detected, with the maximum values ranging from 0.337 to 0.679mg/g. Increasing pH and temperature led to the decline of sorption capacity. Results from three-dimensional excitation-emission matrix fluorescence spectroscopy and Fourier transform infrared spectrometry revealed that amide and carboxyl groups were the main functional groups for TCs adsorption. The interactions between SOM and TCs were clarified as predominated by hydrogen-bonding and cation-exchange in acid conditions, and electrostatic repulsion in neutral or alkaline conditions. Adsorption kinetics modeling was conducted, and a satisfactory fitting was achieved with the Freundlich equation. These results indicated that the adsorption process was a rather complex process, involving a combination of cation-exchange and hydrogen-bonding. The results will provide a better understanding of the capability of SOM for TCs transport and abatement in the wastewater treatment process.

Influences of dissolved organic matters on tetracyclines transport in the process of struvite recovery from swine wastewater.

Due to the extensive existence of tetracyclines (TCs), struvite (MgNH4PO4·6H2O) recovery from swine wastewater will pose TCs-pharmacological threats to the agricultural planting and environment. This study investigated the influences of dissolved organic matters (DOM), as an important medium in the wastewater, on TCs transport during struvite recovery from swine wastewater. Compared to TCs concentrations of 1.49-2.16 µg/g in the solids obtained from synthetic wastewater, the existence of DOM significantly enhanced TCs contents in the products with the values of 360-742 µg/g. DOM was fractionated into four size fractions with different molecular weight cut-off, i.e. FDOM1 (30 kDa-0.45 µm), FDOM2 (5-30 kDa), FDOM3 (1-5 kDa) and FDOM4 (<1 kDa). Results revealed that the destabilization and aggregation of FDOM1 and FDOM2 contributed major roles to TCs transport from the aqueous phase to the solid products. Meanwhile, the hydrolysis of certain parts of FDOM1 and FDOM2 led to the aqueous TCs re-partition among various DOM constituents, which presented a false appearance that FDOM4 with smaller molecular weight posed significant influences on TCs transport. Increasing pH values from 8.5 to 10.5 resulted with a stepwise increase of precipitated DOM, thereby enhancing TCs concentrations from 94.5 to 292.4 µg/g to 627.2-825.0 µg/g in the recovered solids. The outcomes provide a better understanding on the capability of DOM on TCs transport and abatement in the phosphate recovery process.

Application of image processing on struvite recovery from swine wastewater by using the fluidized bed.

Fluidized granulation is one of the common methods used in wastewater treatment and resource recovery with harvesting millimeter-scale large particles. Presently, effective methods are lacking to measure the fluidized granules ranging from micro- to millimeter scales, with the consequence of ineffectively controlling and optimizing the granulation process. In this work, recovering struvite (MgNH4PO4·6H2O) from swine wastewater by using a fluidized bed was taken as an example. Image processing was applied to analyze the properties of different types of struvite granules, including morphology, particle size distribution, number density and mass concentration. Four stages of the struvite crystal evolution were therefore defined: aggregation, aggregate compaction, cluster-agglomerating and coating growth. These stages could occur simultaneously or sequentially. Up-flow rates of 30-80 mm/s in the fluidized bed sustained 600-876 g/L granular solids. Results revealed that the coating-growth granules were formed with compact aggregates or cluster-agglomerating granules as the nuclei. The growth rates for the different types of particles, including population growth, mass increase and particle size enlargement, were determined. In final, a schematic illustration for struvite granulation process is also presented.

Numerical simulation of flow hydrodynamics of struvite pellets in a liquid-solid fluidized bed.

Phosphorus recovery in the form of struvite has been aroused in recent decades for its dual advantages in eutrophication control and resource protection. The usage of the struvite products is normally determined by the size which is largely depended on the hydrodynamics. In this study, flow behavior of struvite pellets was simulated by means of Eulerian-Eulerian two-fluid model combining with kinetic theory of granular flow in a liquid-solid fluidized bed reactor (FBR). A parametric study including the mesh size, time step, discretization strategy, turbulent model and drag model was first developed, followed by the evaluations of crucial operational conditions, particle characteristics and reactor shapes. The results showed that a cold model with the mesh resolution of 16×240, default time step of 0.001sec and first order discretization scheme was accurate enough to describe the fluidization. The struvite holdup profile using Syamlal-O'Brien drag model was best fitted to the experimental data as compared with other drag models and the empirical Richardson-Zaki equation. Regarding the model evaluation, it showed that liquid velocity and particle size played important roles on both solid holdups and velocities. The reactor diameter only influenced the solid velocity while the static bed height almost took no effect. These results are direct and can be applied to guide the operation and process control of the struvite fluidization. Moreover, the model parameters can also be used as the basic settings in further crystallization simulations.