Boron-Modulated Electronic-Configuration Tuning of Cobalt for Enhanced Nitric Oxide Fixation to Ammonia.

Electrocatalytic nitric oxide reduction (eNORR) to ammonia (NH3) provides an environmental route to alleviate NO pollution and yield great-value chemicals. The evolution of eNORR has been primarily hindered, however, by the poor reaction kinetics and low solubility of the NO in aqueous electrolytes. Herein, we have rationally designed a cobalt-based composite with a heterostructure as a highly efficient eNORR catalyst. In addition, by integrating boron to modulate the electronic structure, the catalyst CoB/Co@C delivered a significant NH3 yield of 315.4 µmol h-1 cm-2 for eNORR and an outstanding power density of 3.68 mW cm-2 in a Zn-NO battery. The excellent electrochemical performance of CoB/Co@C is attributed to the enrichment of NO by cobalt and boron dual-site adsorption and fast charge-transfer kinetics. It is demonstrated that the boron is pivotal in the enhancement of NO, the suppression of hydrogen evolution, and Co oxidation to boost eNORR performance.

Enhanced Pseudo-Capacitance Process in Nanoarchitectural Layered Double Hydroxide Nanoarrays Hollow Nanocages for Improved Capacitive Deionization Performance.

Layered double hydroxides (LDHs) are perceived as a hopeful capacitive deionization (CDI) faradic electrode for Cl- insertion due to its tunable composition, excellent anion exchange capacity, and fast redox activity. Nevertheless, the self-stacking and inferior electrical conductivity of the two-dimensional structure of LDH lead to unsatisfactory CDI performance. Herein, the three-dimensional (3D) hollow nanocage structure of CoNi-layered double hydroxide/carbon composites is well designed as a CDI anode by cation etching of the pre-carbonized ZIF-67 template. C/CoNi-LDH has a unique 3D hollow nanocage structure and abundant pore features, which can effectively suppress the self-stacking of LDH sheets and facilitate the transport of ions. Moreover, the introduced amorphous carbon layer can act as a conductive network. When employed as the CDI anode, C/CoNi-LDH exhibited a high Cl- removal capacity of 60.88 mg g-1 and a fast Cl- removal rate of 18.09 mg g-1 min-1 at 1.4 V in 1000 mg L-1 NaCl solution. The mechanism of the Cl- intercalation pseudo-capacitance reaction of C/CoNi-LDH is revealed by electrochemical kinetic analysis and ex situ characterization. This study provides vital guidance for the design of high-performance electrodes for CDI.

Surface redox pseudocapacitance boosting Fe/Fe3C nanoparticles-encapsulated N-doped graphene-like carbon for high-performance capacitive deionization.

The practical application of carbon anode in capacitive deionization (CDI) is greatly hindered by their poor adsorption capacity and co-ion effect. Herein, an N-doped graphene-like carbon (NC) decorated with Fe/Fe3C nanoparticles composite (Fe/Fe3C@NC) with large specific surface area and plentiful porosity is fabricated via a facile and scalable method, namely sol-gel method combined with Fe-catalyzed carbonization. As expected, it exhibits superior CDI performance as a Cl-storage electrode, with Cl- adsorption capacity as high as 102.3 mg g-1 at 1000 mg L-1 Cl- concentration and 1.4 V voltage, and a stable capacity of 68.5 mg g-1 for 60 cycles in 500 mg L-1 Cl- concentration and 100 mA g-1 current density. More importantly, on the basis of electrochemical tests, ex-situ X-ray diffraction, ex-situ X-ray photoelectron spectroscopy (XPS), and XPS analysis with argon ion depth etching, it is revealed that the chlorine storage mechanism of the Fe/Fe3C@NC electrode is dominated by the surface-related redox pseudocapacitance behavior of Fe2+/Fe3+ couple occurring on or near the surface, enabling fast and reversible ion storage. This work proposes an economical and environmentally friendly general method for the design and development of high-performance Cl-storage electrodes for CDI, and offers an in-depth insight into the Cl- storage mechanism of Fe decorated carbon electrodes, further promoting the development of CDI technology.

A Novel Dual-Ion Capacitive Deionization System Design with Ultrahigh Desalination Performance.

Capacitive deionization is an emerging desalination technology with mild operation conditions and high energy efficiency. However, its application is limited due to the low deionization capacity of traditional capacitive electrodes. Herein, we report a novel dual-ion capacitive deionization system with a lithium-ion battery cathode LiMn2O4/C and a sodium-ion battery anode NaTi2(PO4)3/C. Lithium ions could enhance the charge transfer during CDI desalination, while NaTi2(PO4)3/C provided direct intercalation sites for sodium ions. The electrochemical capacities of the battery electrodes fitted well, which was favorable for the optimization of the desalination capacity. The low potential of the redox couple Ti3+/Ti4+ (-0.8 V versus Ag/AgCl) and intercalation/deintercalation behaviors of sodium ions that suppressed hydrogen evolution could enlarge the voltage window of the CDI process to 1.8 V. The novel CDI cell achieved an ultrahigh desalination capacity of 140.03 mg·g-1 at 1.8 V with an initial salinity of 20 mM, revealing a new direction for the CDI performance enhancement.

Carbon Nanoarchitectonics with Bi Nanoparticle Encapsulation for Improved Electrochemical Deionization Performance.

Electrochemical deionization (EDI) is hopefully the next generation of water treatment technology. Bismuth (Bi) is a promising anode material for EDI, due to its high capacity and selectivity toward Cl-, but the large volume expansion and severe pulverization aggressively attenuated the EDI cycling performance of Bi electrodes. Herein, carbon-layer-encapsulated nano-Bi composites (Bi@C) were prepared by a simple pyrolysis method using a Bi-based metal-organic framework as a precursor. Bi nanoparticles are uniformly coated within the carbon layer, in which the Bi-O-C bond enhances the interaction between Bi and C. Such a structure effectively relieves the stress caused by volume expansion by the encapsulation effect of the carbon layer. Moreover, the introduction of a carbon skeleton provides a conductive network. As a consequence, the Bi@C composite delivered excellent electrochemical performance with a capacity of 537.6 F g-1 at 1 mV s-1. The Cl- removal capacity was up to 133.5 mg g-1 at 20 mA g-1 in 500 mg L-1 NaCl solution. After 100 cycles, the Bi@C electrode still maintains 71.8% of its initial capacity, which is much higher than the 26.3% of the pure Bi electrode. This study provides a promising strategy for improving EDI electrode materials.

Proteomic analysis of the reduction and resistance mechanisms of Shewanella oneidensis MR-1 under long-term hexavalent chromium stress.

Hexavalent chromium [Cr(VI)] is a priority heavy metal pollutant causing a series of environmental issues, and bio-reduction of Cr(VI) to trivalent chromium can remarkably decrease the environmental risk of Cr(VI). The reduction and resistance abilities of microorganisms to Cr(VI) can be dramatically improved by acclimatization. In the present study, we collected Shewanella oneidensis MR-1 from a 120-day acclimatization by increasing Cr(VI) concentration in the culture media to investigate its adaptation mechanisms under long-term Cr(VI) stress at the proteome level. Tandem mass tag-based quantitative proteomic analysis was performed to study the differences between 9 collected samples. A total of 2500 proteins were quantified from 2723 identified protein groups. Bioinformatics analysis showed that the differentially expressed proteins after the 120-day Cr(VI) acclimatization were mostly related to flagellar assembly, ribosomes, transport, sulfur metabolism, and energy metabolism. The findings of this study present novel insights into the molecular mechanisms for the reduction and resistance of S. oneidensis MR-1 responding to long-term Cr(VI) stress at the proteome level.

Long-term operation of electroactive biofilms for enhanced ciprofloxacin removal capacity and anti-shock capabilities.

Few studies have focused on the feasibility of microbial fuel cells (MFCs) for removing quinolones antibiotics and their anti-shock capabilities. After 1.5 years of operation, the removal efficiency of 10 mg/L ciprofloxacin in MFCs increased to 99.00% in 88 h. These results are in accordance with the enhanced activity of biofilms and voltage output of MFCs. Additionally, the anti-shock capacities of the biofilms in MFCs were evaluated by treating ofloxacin and enrofloxacin and operating at different temperature and salinity. These MFCs can remove 87.31% and 40.81% of ofloxacin and enrofloxacin in 72 h, respectively. Even exposed to a low temperature of 10 °C or a salinity of 3%, the MFCs can achieve greater than 50% and nearly 80% of ciprofloxacin removal efficiency, respectively. The enrichment of Alcaligenes and Chryseobacterium contributed mostly to the removal of quinolones antibiotics. This study provides scientific evidences for treating wastewater containing quinolones antibiotics using MFCs.

Light-excited photoelectrons coupled with bio-photocatalysis enhanced the degradation efficiency of oxytetracycline.

Intimately coupled photocatalysis and biodegradation (ICPB) is a novel wastewater treatment technique that has potential applications in refractory degradation. This paper reports a synergistic degradation protocol that allowing the transfer of photoelectrons between photocatalysts and microbes without supplementary electron donors or improving the loading rate of the photocatalysts. As a result, a degradation rate of ∼94% was sustained for 400 h in a perturbation setup with a hydraulic retention time of 4.0 h. We achieved the degradation of ß-apo-oxytetracycline, a stable antimicrobial intermediate compound (half-life of 270 d in soil interstitial water), within 10 min, and no accumulation was observed. Moreover, the required loading rate of the photocatalyst was dramatically reduced to 18.3% compared to previous reports which mentioned much higher rates. The results of our study provided a new strategy to improve the degradation efficiency of oxytetracycline and give new insight into the degradation mechanism of the bio-photocatalytic degradation system.

The changes of bacterial communities and antibiotic resistance genes in microbial fuel cells during long-term oxytetracycline processing.

Microbial fuel cell (MFC) is regarded as a promising alternative for enhancing the removal of antibiotic pollutants. In this study, oxytetracycline served as an electron donor in the anode chamber of MFCs, and after continuous operation for 330 days, the efficiency of removal of 10 mg/L oxytetracycline in MFCs increased to 99.00% in 78 h, whereas removal efficiency of only 58.26% was achieved in microbial controls. Compared to microbial controls, higher ATP concentration and persistent electrical stimulation mainly contributed to bioelectrochemical reactions more rapidly to enhance oxytetracycline removal in MFCs. In addition, the analysis of bacterial communities revealed that Eubacterium spp.-as the main functional bacterial genus responsible for oxytetracycline biodegradation-flourished starting from merely 0.00%-91.69% ±â€¯0.27% (mean ±â€¯SD) in MFCs. High-throughput quantitative PCR showed that the normalized copy numbers of total antibiotic resistance genes (ARGs) and mobile genetic elements in MFCs were 1.7364 and 0.0065 copies/cell respectively, which were markedly lower than those in the microbial controls. Furthermore, there was no significant correlation between oxytetracycline concentration in the influent and abundance of ARGs in effluent from MFCs. Nevertheless, Tp614, a transposase gene, was found to be enriched in both MFCs and microbial reactors, suggesting that it may be a common challenge for different biological processes for wastewater treatment. This study therefore showed a lower probability of upregulation and transmission of ARGs in MFCs when compared to a traditional anaerobic microbial treatment.