Mechanism insight into the N-C polar bond and Pd-Co heterojunction for improved hydrogen evolution activity.

Constructing platinum-like materials with excellent catalytic activity and low cost has great significance for hydrogen evolution reaction (HER) during electrolysis of water. Herein, palladium nanoparticles (NPs) deposition on the surface of Co NPs using nitrogen-doped carbon (NC) as substrate, denoted as N-ZIFC/CoPd-30, are manufactured and served as HER electrocatalysts. Characterization results and density functional theory calculations validate that Pd-Co heterojunctions with NC acting as "electron donators" promote the Pd species transiting to the electron-rich state based on an efficient electron transfer mechanism, namely the N-C polar bonds induced strong metal-support interaction effect. The electron-rich Pd sites are beneficial to HER. Satisfactorily, N-ZIFC/CoPd-30 have only low overpotentials of 16, 162, and 13 mV@-10 mA cm-2 with the small Tafel slopes of 98 mV/decade, 126 mV/decade, and 72 mV/decade in pH of 13, 7, and 0, respectively. The success in fabricating N-ZIFC/CoPd opens a promising path to constructing other platinum-like electrocatalysts with high HER activity.

Mechanism insight into double S-scheme heterojunctions and atomic vacancies with tunable band structures for notably enhanced light-driven enrofloxacin decomposition.

Building narrow band gap semiconductors and fast separation of photogenerated electron-hole (e--h+) structures are of great significance for photocatalytic process. In this contribution, the CeO2-x/C3-yN4/Ce(CO3)(OH) double S-scheme heterojunctions with atomic vacancies tunable band gap (2.54 eV) have been designed and fabricated as a boost photocatalyst for enrofloxacin (ENR) photodegradation. Compared with the control samples, the experimental results indicate that the typical sample (CeO2-x/C3-yN4/Ce(CO3)(OH)-2) achieves the highest ENR photodegradation efficiency (93.6 %) in 240 min under a pH of 6, and the possible photodegradation pathways are also proposed. The superior performance is ascribed to the CeO2-x/C3-yN4/Ce(CO3)(OH) double S-scheme heterojunctions for selective recombination of photogenerated electrons with weak-reduction ability in conduction band (CB) of CeO2-x, C3-yN4 and the photogenerated holes with weak-oxidation nature in valance band (VB) of C3-yN4, Ce(CO3)(OH), which increase the retention rate of photogenerated electrons in CB of Ce(CO3)(OH) and photogenerated holes in VB of CeO2-x to degrade ENR. This is the first systematic study of CeO2-x/C3-yN4/Ce(CO3)(OH) double S-scheme heterojunctions for ENR photodegradation.

Preparation of Yb-Sb co-doped Ti/SnO2 electrode for electrocatalytic degradation of sulfamethoxazole (SMX).

To efficiently break down residual sulfonamide antibiotics in environmental water, Yb-Sb co-doped Ti/SnO2 electrodes were fabricated using a solvothermal method. The effect of different amounts of Yb doping on the properties of the electrodes was studied. When the atom ratio of Sn: Yb is 100 : 7.5 in the preparation, the as-obtained coral-like electrodes (denoted as Yb 7.5%) possessed the smallest diameter of spherical particles on the surfaces, to result in the denser surface, highest electrocatalytic activity and smallest resistance of the electrode. As anode for electrocatalytic degradation of sulfamethoxazole, the Yb 7.5% electrode showed a degradation rate of 92% in 90 min, which was much higher than that of Yb 0% electrode (62.7% degradation rate). The electrocatalytic degradation of sulfamethoxazole was investigated with varying current densities and initial concentrations. Results indicated that the degradation process followed pseudo-first-order kinetics, and the degradation rate constants for Yb 7.5% and Yb 0% electrodes were 0.0278 min-1 and 0.0114 min-1, respectively. Furthermore, the service life of Ti/SnO2 electrodes was significantly improved after Yb doping, as demonstrated by accelerated life testing. Yb 7.5% exhibited a service life that was 2.7 times longer than that of Yb 0%. This work offers a new approach to construct Yb-Sb co-doped Ti/SnO2 electrodes with excellent electrooxidation activity and high stability for the electrochemical oxidation degradation of sulfamethoxazole.

Separation of Hydrochloric Acid and Oxalic Acid from Rare Earth Oxalic Acid Precipitation Mother Liquor by Electrodialysis.

In this study, the hydrochloric acid from rare earth oxalic acid precipitation mother liquor was separated by electrodialysis (ED) with different anion exchange membranes, including selective anion exchange membrane (SAEM), polymer alloy anion exchange membrane (PAAEM), and homogenous anion exchange membrane (HAEM). In addition to actual wastewater, nine types of simulated solutions with different concentrations of hydrochloric acid and oxalic acid were used in the experiments. The results indicated that the hydrochloric acid could be separated effectively by electrodialysis with SAEM from simulated and real rare earth oxalic acid precipitation mother liquor under the operating voltage 15 V and ampere 2.2 A, in which the hydrochloric acid obtained in the concentrate chamber of ED is of higher purity (>91.5%) generally. It was found that the separation effect of the two acids was related to the concentrations and molar ratios of hydrochloric acid and oxalic acid contained in their mixtures. The SEM images and ESD-mapping analyses indicated that membrane fouling appeared on the surface of ACS and CSE at the diluted side of the ED membrane stack when electrodialysis was used to treat the real rare earth oxalic acid precipitation mother liquor. Fe, Yb, Al, and Dy were found in the CSE membrane section, and organic compounds containing carbon and sulfur were attached to the surface of the ACS. The results also indicated that the real rare earth precipitation mother liquor needed to be pretreated before the separation of hydrochloric acid and oxalic acid by electrodialysis.

Novel B and N Sites of One-Dimensional Boron Nitride Fiber: Efficient Performance and Mechanism in the Formaldehyde Capture Process.

Identification of adsorption centers with atomic levels of adsorbents is crucial to study the adsorption of formaldehyde (HCHO), especially for an in-depth understanding of the mechanism of HCHO capture. Herein, we investigate the HCHO adsorption performance of one-dimensional (1D) nanoporous boron nitride (BN) fiber, and explore the adsorption mechanism by density functional theory (DFT) calculations, including adsorption energy change and Bader charge change, and experimental study as well. Research shows that the 1D nanoporous BN fiber possesses a high concentration of Lewis pairs, which act as Lewis acid and Lewis base sites associated with the fiber's electron-deficient and electron-rich features. It is worth noting that the HCHO removal efficiency of a typical sample is as high as 91%. This work may open the door to the field of adsorption of other pollutants by constructing Lewis pairs in the future.

Bipolar Membrane Electrodialysis for Ammonia Recovery from Synthetic Urine: Experiments, Modeling, and Performance Analysis.

Recovering nitrogen from source-separated urine is an important part of the sustainable nitrogen management. A novel bipolar membrane electrodialysis with membrane contactor (BMED-MC) process is demonstrated here for efficient recovery of ammonia from synthetic source-separated urine (∼3772 mg N L-1). In a BMED-MC process, electrically driven water dissociation in a bipolar membrane simultaneously increases the pH of the urine stream and produces an acid stream for ammonia stripping. With the increased pH of urine, ammonia transports across the gas-permeable membrane in the membrane contactor and is recovered by the acid stream as ammonium sulfate that can be directly used as fertilizer. Our results obtained using batch experiments demonstrate that the BMED-MC process can achieve 90% recovery. The average ammonia flux and the specific energy consumption can be regulated by varying the current density. At a current density of 20 mA cm-2, the energy required to achieve a 67.5% ammonia recovery in a 7 h batch mode is 92.8 MJ kg-1 N for a bench-scale system with one membrane stack and can approach 25.8 MJ kg-1 N for large-scale systems with multiple membrane stacks, with an average ammonia flux of 2.2 mol m-2 h-1. Modeling results show that a continuous BMED-MC process can achieve a 90% ammonia recovery with a lower energy consumption (i.e., 12.5 MJ kg-1 N). BMED-MC shows significant potential for ammonia recovery from source-separated urine as it is relatively energy-efficient and requires no external acid solution.

Comparative studies on fouling of homogeneous anion exchange membranes by different structured organics in electrodialysis.

Five negatively charged organic compounds with different structures, sodium methane sulfonate (MS), sodium benzene sulfonate (BS), sodium 6-hydroxynaphthalene-2-sulfonate (NSS), sodium dodecyl sulfate (SDS), and sodium dodecyl benzene sulfonate (SDBS), were used to examine the fouling of an anion exchange membrane (AEM) in electrodialysis (ED), to explore the effect of molecular characteristics on the fouling behavior on the AEM and changes in the surface and electrochemical properties of the AEM. Results indicated that the fouling degree of the AEM by the different organics followed the order: SDBS > SDS > NSS > BS > MS. SDBS and SDS formed a dense fouling layer on the surface of the AEM, which was the main factor in the much more severe membrane fouling, and completely restricted the transmembrane ion migration. The other three organics caused fouling of the AEM by adsorption on the surface and /or accumulation in the interlayer of the AEM, and exhibited almost no influence on the transmembrane ion migration. It was also concluded that the organics with benzene rings caused more severe fouling of the AEM due to the stronger affinity interaction and steric effect between the organics and the AEM compared with organics with aliphatic chains.

Bipolar membrane electrodialysis for generation of hydrochloric acid and ammonia from simulated ammonium chloride wastewater.

Simulated ammonium chloride wastewater was treated by a lab-scale bipolar membrane electrodialysis for the generation of HCl and NH3·H2O and desalination. The influence of initial concentration of NH4Cl, current density, salt solution volume, initial concentration of acid and base and membrane stack structure on the yields of HCl and NH3·H2O was investigated. The current efficiency and energy consumption were also examined under different conditions. The results showed that, at the current density of 48 mA/cm(2), the highest concentration of HCl and NH3·H2O with initial concentration of 110 g/L NH4Cl was 57.67 g/L and 45.85 g/L, respectively. Higher initial concentration of NH4Cl was favor to reduce unit energy consumption and increase current efficiency of the BMED system. The membrane stack voltage of BMED increased quickly under constant current when the concentration of NH4Cl contained in the solution of salt compartment was depleted below the "inflection point concentration" about 8000 mg/L. It means that the concentration of NH4Cl below 8000 mg/L was no longer suitable for BMED because of higher energy consumption. The HCl and NH3·H2O concentration increased more quickly following the increase of current density. When increasing the volume of NH4Cl, the concentration of HCl and NH3·H2O also increased. The high initial concentration of acid and base could improve the final concentration of them, while the growth rate was decreased. Compared with the BMED system with three compartments, the growth rate of HCl concentration with the two compartments was higher and its unit energy consumption was lower. It meant that the performance of the BMED system could be improved by optimizing operation conditions. The application feasibility of the generation of HCl and NH3·H2O and desalination of ammonium chloride wastewater by BMED was proved.

Application of a pH feedback-controlled substrate feeding method in lactic acid production.

Substrate concentration in lactic acid fermentation broth could not be controlled well by traditional feeding methods, including constant, intermittent, and exponential feeding methods, in fed-batch experiments. A simple feedback feeding method based on pH was proposed to control pH and substrate concentration synchronously to enhance lactic acid production in fed-batch culture. As the linear relationship between the consumption amounts of alkali and that of substrate was concluded during lactic acid fermentation, the alkali and substrate in the feeding broth were mixed together proportionally. Thus, the concentration of substrate could be controlled through the adjustment of pH automatically. In the fed-batch lactic acid fermentation with Lactobacillus lactis-11 by this method, the residual glucose concentration in fermentation broth was controlled between 4.1 and 4.9 g L⁻¹, and the highest concentration of lactic acid, maximum cell dry weight, volumetric productivity of lactic acid, and yield were 96.3 g L⁻¹, 4.7 g L⁻¹, 1.9 g L⁻¹ h⁻¹, and 0.99 g lactic acid per gram of glucose, respectively, compared to 82.7 g L⁻¹, 3.31 g L⁻¹, 1.7 g L⁻¹ h⁻¹, and 0.92 g lactic acid per gram of glucose in batch culture. This feeding method was simple and easily operated and could be feasible for industrial lactic acid production in the future.

An effective device for gas-liquid oxygen removal in enclosed microalgae culture.

A high-performance gas-liquid transmission device (HPTD) was described in this paper. To investigate the HPTD mass transfer characteristics, the overall volumetric mass transfer coefficients, K(A)(La,CO(2)) for the absorption of gaseous CO(2) and K(A)(La,O(2)) for the desorption of dissolved O(2) were determined, respectively, by titration and dissolved oxygen electrode. The mass transfer capability of carbon dioxide was compared with that of dissolved oxygen in the device, and the operating conditions were optimized to suit for the large-scale enclosed micro-algae cultivation. Based on the effectiveness evaluation of the HPTD applied in one enclosed flat plate Spirulina culture system, it was confirmed that the HPTD can satisfy the demand of the enclosed system for carbon supplement and excessive oxygen removal.

Essential explanation of the strong mineralization performance of boron-doped diamond electrodes.

Electrochemical oxidation of p-nitrophenol was examined using differentanodic materials, including T/boron-doped diamond (BDD), Ti/SnO2-Sb/PbO2, and Ti/SnO2-Sb anodes. The results demonstrated that Ti/BDD anodes had a much stronger mineralization performance than the other two anodes. Furthermore, it was found that hydroxyl radicals could mainly exist as free hydroxyl radicals at BDD anodes, which could react with organic compounds effectively. This implied that the dominant mechanism for a much higher mineralization capacity of BDD anodes would be attributed to the existence of free hydroxyl radicals in the BDD anode cell rather than adsorbed hydroxyl radicals on the BDD anode. To further corroborate this hypothesis, electrochemical oxidation of p-substituted phenols (p-nitrophenol, p-hydroxybenzaldehyde, phenol, p-cresol, and p-methoxyphenol) was examined at the Ti/BDD, Ti/SnO2-Sb/ PbO2, and Ti/SnO2-Sb anodes, respectively. The study revealed that for Ti/BDD electrodes, the degradation rate of p-substituted phenols (k) increased with the increase of Hammett's constant (sigma), which confirmed the dominance of free hydroxyl radicals at BDD anodes and its effective reaction with organics therein. For Ti/SnO2-Sb/PbO2 electrodes, the degradation rate of p-substituted phenols (k) increased with the increase of initial surface concentration gamma (representing the adsorption capacity of phenols to electrode surface), which indicated that organic compounds mainly reacted with adsorbed hydroxyl radicals at PbO2 anodes. For Ti/SnO2-Sb electrodes, however, k increased with the increase of the integrated parameter S (representing the effects of both sigma and gamma), which implied that organic compounds reacted with both adsorbed hydroxyl radicals and free hydroxyl radicals at SnO2 anodes.

An economical device for carbon supplement in large-scale micro-algae production.

One simple but efficient carbon-supplying device was designed and developed, and the correlative carbon-supplying technology was described. The absorbing characterization of this device was studied. The carbon-supplying system proved to be economical for large-scale cultivation of Spirulina sp. in an outdoor raceway pond, and the gaseous carbon dioxide absorptivity was enhanced above 78%, which could reduce the production cost greatly.

Electrochemical oxidation characteristics of p-substituted phenols using a boron-doped diamond electrode.

Electrochemical oxidation of some p-substituted phenols (p-nitrophenol, p-hydroxybenzaldehyde, phenol, p-cresol, and p-methoxyphenol) with electron-donating and -withdrawing substituents was studied to reveal the relationship between the structure and the electrochemical reactivity of p-substituted phenols using a boron-doped diamond electrode by voltammetry and bulk electrolysis. Voltammetric study shows that the oxidation peak potentials of p-substituted phenols become more positive with an increase of Hammett's constants, that is, the direct electrochemical oxidation of p-substituted phenol with an electron-withdrawing group is more difficult than that of p-substituted phenol with an electron-donating group. However,the p-substituted phenols with electron-withdrawing groups are degraded faster than those with electron-donating groups in bulk electrolysis, which is opposite to the result obtained on the Pt electrode. These results indicate that the p-substituted phenols are mainly degraded by indirect electrochemical oxidation with hydroxyl radicals on a boron-doped diamond electrode. Under the attack of hydroxyl radicals, the release of p-substituted groups from the aromatic ring is the rate-limiting step. Since electron-withdrawing groups are easy to be released, the p-substituted phenols with these groups are degraded faster than those with electron-donating groups. Therefore, the degradation rates of the p-substituted phenols rise with an increase of Hammett's constants.

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO2 electrodes in the oxidation of 4-chlorophenol.

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction (XRD). The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

Electrochemistry of marmatite-carbon paste electrode in the presence of bacterial strains.

The electrochemical behaviors of a marmatite-carbon paste electrode with the chemical leaching of Fe3+ ions, or the microbial leaching using Acidithiobacillus ferrooxidans, were compared. The cyclic voltammograms of the electrode in the presence and absence of bacterial strains showed that the leaching process of marmatite was carried out by the different reactions occurring in the interface of the marmatite electrode-leach liquid. The polarization currents of the electrode under the differently applied potentials suggested that the microbial leaching of marmatite could be accelerated by the applied potential. The SEM observations indicated that the corrosion pits formed in the electrode surface were similar to the attached bacterial cells in shape and size, other than that by the chemical leaching of Fe3+ ions. The contact leaching of the attached cells on the mineral substrate played an important role on the dissolution of marmatite in addition to the chemical leaching of Fe3+ ions.