Electrochemical Enrichment Research Articles

Electrochemical enrichment of a community of weak electricigens and characterisation of three halotolerant electroactive isolates: Micrococcus sp. YH-1, Gordonia sp. RH-1 and Stutzerimonas sp. CH-1

Microbial electroactivity in elevated salt conditions is seldom studied, despite both fundamental and applied relevance. This work reports the enrichment of electroactive microorganisms under saline conditions (2% NaCl), performed on screen-printed carbon electrodes with applied anodic potential. From the weakly electroactive enriched community, three halotolerant electroactive isolates were obtained in pure culture and identified via 16S rRNA gene sequencing. Two isolates were Gram positive (proposed names Micrococcus sp. YH-1 and Gordonia sp. RH-1) and one was Gram negative (proposed name Stutzerimonas sp. CH-1). The isolates were electrochemically characterised on conventional carbon felt electrodes using chronoamperometry. After two days of growth, a current density of 8.29 ± 0.85 μA/cm2 was observed in Micrococcus sp. YH-1, comparable to reported values for the model electroactive microorganism Shewanella oneidensis. Gordonia sp. RH-1 and Stutzerimonas sp. CH-1 appeared to be weak electricigens due to their low current output (2.19 ± 0.46 μA/cm2 and 1.73 ± 0.47 μA/cm2, respectively). The isolates are notable as there are very limited reports of electroactivity in the genera Micrococcus and Gordonia. Cyclic voltammetry revealed prominent redox peaks in Micrococcus sp. YH-1 and Stutzerimonas sp. CH-1. Scanning electron microscopy demonstrated colonisation of the electrode by each isolate, along with thin cellular appendages in Micrococcus sp. YH-1 and Stutzerimonas sp. CH-1. This work extends the catalogue of characterised halotolerant electroactive microbes while also enhancing our understanding of weak electricigens, extracellular electron transfer in Gram positives, and the inherent electroactivity of the natural environment.

Electrochemical Enrichment of Biocharcoal Modified on Carbon Electrodes for the Detection of Nitrite and Paraxon Ethyl Pesticide

Biocharcoal (BioC), a cost-effective, eco-friendly, and sustainable material can be derived from various organic sources including agricultural waste. However, to date, complex chemical treatments using harsh solvents or physical processes at elevated temperatures have been used to activate and enhance the functional groups of biochar. In this paper, we propose a novel easy and cost-effective activation method based on electrochemical cycling in buffer solutions to enhance the electrochemical performance of biocharcoal derived from almond shells (AS-BioC). The novel electrochemical activation method enhanced the functional groups and porosity on the surface of AS-BioC, as confirmed by microscopic, spectroscopic characterizations. Electrochemical characterization indicated an increase in the conductivity and surface area. A modified SPCE with activated AS-BioC (A.AS-BioC/SPCE), shows enhanced electrochemical performance towards oxidation and reduction of nitrite and paraxon ethyl pesticide, respectively. For both target analytes, the activated electrode demonstrates high electrocatalytic activity and achieves a very LOD of 0.38 µM for nitrite and 1.35 nM for ethyl paraxon with a broad linear range. The sensor was validated in real samples for both contaminants. Overall, the research demonstrates an innovative technique to improve the performance of AS-BioC to use as a modifier material for electrochemical sensors.

Electrochemical Enrichment and Isolation of Electrogenic Bacteria from 0.22 µm Filtrate.

Ultramicrobacteria (UMB) that can pass through a 0.22 µm filter are attractive because of their novelty and diversity. However, isolating UMB has been difficult because of their symbiotic or parasitic lifestyles in the environment. Some UMB have extracellular electron transfer (EET)-related genes, suggesting that these symbionts may grow on an electrode surface independently. Here, we attempted to culture from soil samples bacteria that passed through a 0.22 µm filter poised with +0.2 V vs. Ag/AgCl and isolated Cellulomonas sp. strain NTE-D12 from the electrochemical reactor. A phylogenetic analysis of the 16S rRNA showed 97.9% similarity to the closest related species, Cellulomonas algicola, indicating that the strain NTE-D12 is a novel species. Electrochemical and genomic analyses showed that the strain NTE-D12 generated the highest current density compared to that in the three related species, indicating the presence of a unique electron transfer system in the strain. Therefore, the present study provides a new isolation scheme for cultivating and isolating novel UMB potentially with a symbiotic relationship associated with interspecies electron transfer.

Enhanced nitrogen and carbon removal in natural seawater by electrochemical enrichment in a bioelectrochemical reactor

Municipal and industrial wastewater discharges in coastal and marine environments are of major concern due to their high carbon and nitrogen loads and the resulted phenomenon of eutrophication. Bioelectrochemical reactors (BERs) for simultaneous nitrogen and carbon removal have gained attention owing to their cost efficiency and versatility, as well as the possibility of electrochemical enrich specific groups. This study presented a scalable two-chamber BERs using graphite granules as electrode material. BERs were inoculated and operated for 37 days using natural seawater with high concentrations of ammonium and acetate. The BERs demonstrated a maximum current density of 0.9 A m−3 and removal rates of 7.5 mg NH4+-N L−1 d−1 and 99.5 mg L−1 d−1 for total organic carbon (TOC). Removals observed for NH4+-N and TOC were 96.2% and 68.7%, respectively. The results of nutrient removal (i.e., ammonium, nitrate, nitrite and TOC) and microbial characterization (i.e., next-generation sequencing of the 16S rRNA gene and fluorescence in situ hybridization) showed that BERs operated with a poised cathode at −260 mV (vs. Ag/AgCl) significantly enriched nitrifying microorganisms in the anode and denitrifying microorganisms and planctomycetes in the cathode. Interestingly, the electrochemical enrichment did not increase the total number of microorganisms in the formed biofilms but controlled their composition. Thus, this work shows the first successful attempt to electrochemically enrich marine nitrifying and denitrifying microorganisms and presents a technique to accelerate the start-up process of BERs to remove dissolved inorganic nitrogen and total organic carbon from seawater.

Highly Sensitive Electrochemical Determination of Lead(II) by Double Stranded DNA (dsDNA) with a Carbon Paper/Reduced Graphene Oxide (CP/rGO) Substrate by Differential Pulse Anodic Stripping Voltammetry (DPASV)

Lead pollution may cause serious damage to environment safety and human health, especially to children’s growth. In this work, by using double stranded DNA (dsDNA) as the recognition element, a simple and effective electrochemical DNA sensor has been developed on a full carbon-based substrate, reduced graphene oxide/carbon paper (rGO/CP), to accomplish the rapid, sensitive and selective determination of Pb2+. Carbon paper (CP) provides a suitable substrate for the sensor with high portability and low cost, while rGO is easily electrodeposited onto CP and serves as both the signal amplification element and the molecular bridge between DNA and CP. Because of its high specific surface area and unique conjugated giant π structure, rGO tightly binds with DNA through π-π stacking and hydrophobic interactions, thereby providing loading of high quantities of DNA. The specific coordination between DNA and Pb2+ further improves the sensitivity of the sensor. The results demonstrate that rapid electrochemical enrichment of Pb2+ is achieved using the constructed CP/rGO/DNA electrode with a linear relationship between the peak current and the concentration of Pb2+ from 1 pM to 100 pM and a detection limit of 1 pM. In addition, this approach shows good selectivity and satisfactory repeatability for river water analysis. A promising sensitive, low-cost, simply-fabricated, and portable full carbon-based electrochemical biosensing platform has been therefore provided for lead determination.

Bioelectricity Buzz.

Bioelectricity Buzz.

The protonated 2 × 4 tunnel manganese oxide nanobelts for high-efficient electrochemical rubidium enrichment

Octahedral molecular sieve – 5 (OMS-5), a typical 2 × 4 tunnel manganese oxide, is considered as an adsorbent for rubidium ion (Rb+) because of its specific tunnel structure. Also, manganese oxide-based nanomaterials are also widely used in supercapacitor energy storage and capacitor deionization electrodes due to their high specific capacitance. In this work, a series of protonated OMS-5 (H-OMS-5, H-Co-OMS-5, and H-Ni-OMS-5) nanobelts are synthesized and used as electrode materials for electrochemical enrichment of Rb+ in aqueous solution. The specific capacity values for H-OMS-5, H-Co-OMS-5, and H-Ni-OMS-5 at 1 A·g−1 are of 159, 168, and 215 F·g−1, respectively. Thanks to the unique protonated 2 × 4 tunnel structure, well regulating surface area, and excellent specific capacitance, the maximum Rb+ adsorption capacities of H-OMS-5, H-Co-OMS-5, and H-Ni-OMS-5 can reach to 390.3, 405.7, and 481.7 mg·g−1, respectively. These results indicate that the protonated 2 × 4 tunnel manganese dioxide nanobelts are of great potentials as faradaic electrode materials for selective rubidium ion enrichment applications.

Disentangling the syntrophic electron transfer mechanisms of Candidatus geobacter eutrophica through electrochemical stimulation and machine learning

Interspecies hydrogen transfer (IHT) and direct interspecies electron transfer (DIET) are two syntrophy models for methanogenesis. Their relative importance in methanogenic environments is still unclear. Our recent discovery of a novel species Candidatus Geobacter eutrophica with the genetic potential of IHT and DIET may serve as a model species to address this knowledge gap. To experimentally demonstrate its DIET ability, we performed electrochemical enrichment of Ca. G. eutrophica-dominating communities under 0 and 0.4 V vs. Ag/AgCl based on the presumption that DIET and extracellular electron transfer (EET) share similar metabolic pathways. After three batches of enrichment, Geobacter OTU650, which was phylogenetically close to Ca. G. eutrophica, was outcompeted in the control but remained abundant and active under electrochemical stimulation, indicating Ca. G. eutrophica’s EET ability. The high-quality draft genome further showed high phylogenomic similarity with Ca. G. eutrophica, and the genes encoding outer membrane cytochromes and enzymes for hydrogen metabolism were actively expressed. A Bayesian network was trained with the genes encoding enzymes for alcohol metabolism, hydrogen metabolism, EET, and methanogenesis from dominant fermentative bacteria, Geobacter, and Methanobacterium. Methane production could not be accurately predicted when the genes for IHT were in silico knocked out, inferring its more important role in methanogenesis. The genomics-enabled machine learning modeling approach can provide predictive insights into the importance of IHT and DIET.

Electrochemical enrichment of haloalkaliphilic nitrate-reducing microbial biofilm at the cathode of bioelectrochemical systems

SummaryElectrotrophic microorganisms have not been well studied in extreme environments. Here, we report on the nitrate-reducing cathodic microbial biofilm from a haloalkaline environment. The biofilm enriched via electrochemical approach under 9.5 pH and 20 g NaCl/L salinity conditions achieved current density and nitrate reduction efficiency via partial and complete denitrification. Voltammetric characterization of the biocathodes revealed a redox center with (vs. Ag/AgCl) formal potential putatively involved in the electron uptake process. The lack of soluble redox mediators and hydrogen-driven nitrate reduction suggests direct-contact cathodic electron uptake by the nitrate-reducing microorganisms in the enriched biofilm. 16S-rRNA amplicon sequencing of the cathodic biofilm revealed the presence of unreported Pseudomonas, Natronococcus, and Pseudoalteromonas spp. at , and relative sequence abundances, respectively. The enriched nitrate-reducing microorganisms also reduced nitrate efficiently using soluble electron donors found in the lake sediments, thereby suggesting their role in N-cycling in such environments.

Electrochemical enrichment of marine denitrifying bacteria to enhance nitrate metabolization in seawater

High concentrations of nitrate from industrial discharges to coastal marine environments are a matter of concern owing to their ecological consequences. In the last years, Bioelectrochemical Denitrification Systems (BEDS) have emerged as a promising nitrate removal technology. However, they still have limitations, such as the enrichment strategy for specific microbial communities in the electrodes under natural conditions. In this study, three-electrode electrochemical cells were used to test microbial enrichment from natural seawater by applying three reported potentials associated with the dissimilatory denitrification process (−130, −260, and −570 mV vs. Ag/AgCl). The microbial community analysis showed that by applying −260 mV (vs. Ag/AgCl) to the working electrode, it was possible to significantly enrich denitrifying microorganisms, specifically Marinobacter, in comparison with the control. Furthermore, −260 mV (vs. Ag/AgCl) led to a significantly higher nitrate removal than other conditions, which, combined with cyclic voltammetry analysis, suggested that the polarized electrodes worked as external electron donors for nitrate reduction. Hence, this work demonstrates for the first time that it is possible to enrich marine denitrifying microorganisms by applying an overpotential of −260 mV (vs. Ag/AgCl) without the need for a culture medium, the addition of an exogenous electron donor (i.e., organic matter) or a previously enriched inoculum.

Electroactive microorganisms in mouse feces

The gut microbiome is not only an indicator of different pathologies, but it also influences metabolism and overall health of the host. Recently, microorganisms inherent to the gut microbiome, such as Listeria monocytogenes, Enterococcus faecalis and Clostridium cochlearium, were demonstrated to be electroactive, i.e. to perform extracellular electron transfer (EET). To further explore the presence of electroactive microorganisms in the gut microbiome electrochemical enrichment starting from mouse feces was performed. Open circuit, abiotic and autoclaved inoculum controls were run in parallel. A maximum current density of 122±23 µA cm−2 at low coulombic efficiency ( ̴1%) was achieved. The presence of biofilms at the anode and microbial electrochemical activity with a formal potential of EET of 0.23±0.01 V vs. Ag/AgCl sat. KCl was demonstrated using fluorescence microscopy and cyclic voltammetry. The 16S rRNA gene sequencing and PCR-free Nanopore sequencing showed the enrichment and dominance of Shigella flexneri.

Electrochemical Bacterial Enrichment from Natural Seawater and Its Implications in Biocorrosion of Stainless-Steel Electrodes.

Microbial electrochemical technologies have revealed the opportunity of electrochemical enrichment for specific bacterial groups that are able to catalyze reactions of interest. However, there are unsolved challenges towards their application under aggressive environmental conditions, such as in the sea. This study demonstrates the impact of surface electrochemical potential on community composition and its corrosivity. Electrochemical bacterial enrichment was successfully carried out in natural seawater without nutrient amendments. Experiments were carried out for ten days of exposure in a closed-flow system over 316L stainless steel electrodes under three different poised potentials (−150 mV, +100 mV, and +310 mV vs. Ag/AgCl). Weight loss and atomic force microscopy showed a significant difference in corrosion when +310 mV (vs. Ag/AgCl) was applied in comparison to that produced under the other tested potentials (and an unpoised control). Bacterial community analysis conducted using 16S rRNA gene profiles showed that poised potentials are more positive as +310 mV (vs. Ag/AgCl) resulted in strong enrichment for Rhodobacteraceae and Sulfitobacter. Hence, even though significant enrichment of the known electrochemically active bacteria from the Rhodobacteraceae family was accomplished, the resultant bacterial community could accelerate pitting corrosion in 316 L stainless steel, thereby compromising the durability of the electrodes and the microbial electrochemical technologies.

Polyacrylamide/Phytic Acid/Polydopamine Hydrogel as an Efficient Substrate for Electrochemical Enrichment of Circulating Cell-Free DNA from Blood Plasma.

A facile method has been developed for the rapid and efficient enrichment of DNAs from different media including synthetic single-strand DNAs (ssDNAs) from buffer solutions and cell-free DNAs (cfDNAs) from blood plasma through electric field-driven adsorption and desorption of DNAs by a polyacrylamide/phytic acid/polydopamine (PAAM/PA/PDA) hydrogel. The as-prepared PAAM/PA/PDA hydrogel possesses regular porosity with a large surface area, strong electric field responsiveness/good conductivity, and a rich aromatic structure, which can be used as an ideal adsorbent for DNA enrichment under a positive electric field. The enriched DNAs can be released efficiently when the positive electric field is converted to a negative electric field. The PAAM/PA/PDA hydrogel-based electrochemical method enables the completion of the process of DNA adsorption and release within 5 min and exhibits reasonable enrichment efficiencies and recovery rates of various DNAs. For instance, the high enrichment sensitivity (0.1 pmol L–1) together with the excellent recovery (>75%) of an ssDNA with 78 nucleotides is obtained. Combined with the PCR amplification technique, the practicability of the as-proposed method is demonstrated by the screening of circulating tumor DNAs (ctDNAs) with a BRAFV600E mutation in cfDNAs from the blood plasma samples of patients with papillary thyroid cancer or thyroid nodule and random patients from a clinical laboratory.

Highly sensitive and stable analysis of trace arsenic(III) and mercury(II) in water by Low-pulse-energy (15 mJ) laser-induced breakdown spectroscopy assisted by active controllable spark discharge and electrochemical enrichment

Laser-induced breakdown spectroscopy (LIBS) has emerged as promising technology in view of its unique advantages and application in analysis of environmental samples. However, such a method encounters significant challenges in detecting arsenic and mercury, which are prone to volatilization at high pulse energy. Herein, a new approach, low-pulse-energy LIBS supported by active controllable spark discharge and electrochemical enrichment is proposed to overcome the above problems. In this approach, a low pulse energy (15 mJ) instead of high pulse energy (typically 100 mJ) reported in previous work was applied to reducing the volatilization of arsenic and mercury as well as downsizing ablation spot of the sample. The temperature on the samples with pulse energy of 15 mJ, which was simulated with MATLAB, was more than 5 times lower than that of 100 mJ. Active controllable spark discharge makes up for the insufficiency in the content of excited arsenic or mercury plasma resulting from low pulse energy (15 mJ) and especially supplies a stable plasma source. As a result, a high sensitivity of 3.35 counts ppb-1, low limit of detection of 8.69 ppb and excellent stability (relative standard deviation is lower than 5 %) for arsenic(III) were exhibited. Efficient and fast preconcentration of arsenic(III) is achieved by electrochemical enrichment on the electrode modified using flower-like NiCo2O4-x-NH2 nanosheets with regulable oxygen vacancies. This method provides an opportunity to detect volatile arsenic(III) and mercury(II), as well as heavy metal ions (HMIs) hard to volatilize, such as copper(II). It’s an effective new method for detecting HMIs.

In situ Electrochemical Studies of the Terrestrial Deep Subsurface Biosphere at the Sanford Underground Research Facility, South Dakota, USA

The terrestrial deep subsurface is host to significant and diverse microbial populations. However, these microbial populations remain poorly characterized, partially due to the inherent difficulty of sampling, in situ studies, and isolating of the in situ microbes. Motivated by the ability of microbes to gain energy from redox reactions at mineral interfaces, we here present in situ electrochemical colonization (ISEC) reactor as a method to directly study microbial electron transfer activity and to enable the capture and isolation of electrochemically active microbes. We installed a potentiostatically controlled ISEC reactor containing four working electrodes 1500 m below the surface at the Sanford Underground Research Facility. The working electrodes were poised at different redox potentials to mimic energy-yielding mineral reducing and oxidizing reactions predicted to occur at this site. We present a 16S rRNA analysis of the in situ electrode-associated microbial communities, revealing the dominance of novel bacterial lineages under cathodic conditions. We also demonstrate that the in situ electrodes can be further used for downstream electrochemical laboratory enrichment and isolation of novel strains. Using this workflow, we isolated Bacillus, Anaerospora, Comamonas, Cupriavidus, and Azonexus strains from the electrode-attached biomass. Finally, the extracellular electron transfer activity of Comamonas strain (isolated at -0.19 V vs. SHE and designated WE1-1D1) and Bacillus strain (isolated at +0.53 V vs. SHE and designated WE4-1A1-BC) from and to a poised electrode, respectively, were confirmed in electrochemical reactors. Our study highlights the utility of in situ electrodes and electrochemical enrichment workflows to shed light on microbial activity in the deep terrestrial subsurface.

Differences in Applied Redox Potential on Cathodes Enrich for Diverse Electrochemically Active Microbial Isolates From a Marine Sediment.

The diversity of microbially mediated redox processes that occur in marine sediments is likely underestimated, especially with respect to the metabolisms that involve solid substrate electron donors or acceptors. Though electrochemical studies that utilize poised potential electrodes as a surrogate for solid substrate or mineral interactions have shed some much needed light on these areas, these studies have traditionally been limited to one redox potential or metabolic condition. This work seeks to uncover the diversity of microbes capable of accepting cathodic electrons from a marine sediment utilizing a range of redox potentials, by coupling electrochemical enrichment approaches to microbial cultivation and isolation techniques. Five lab-scale three-electrode electrochemical systems were constructed, using electrodes that were initially incubated in marine sediment at cathodic or electron-donating voltages (five redox potentials between −400 and −750 mV versus Ag/AgCl) as energy sources for enrichment. Electron uptake was monitored in the laboratory bioreactors and linked to the reduction of supplied terminal electron acceptors (nitrate or sulfate). Enriched communities exhibited differences in community structure dependent on poised redox potential and terminal electron acceptor used. Further cultivation of microbes was conducted using media with reduced iron (Fe0, FeCl2) and sulfur (S0) compounds as electron donors, resulting in the isolation of six electrochemically active strains. The isolates belong to the genera Vallitalea of the Clostridia, Arcobacter of the Epsilonproteobacteria, Desulfovibrio of the Deltaproteobacteria, and Vibrio and Marinobacter of the Gammaproteobacteria. Electrochemical characterization of the isolates with cyclic voltammetry yielded a wide range of midpoint potentials (99.20 to −389.1 mV versus Ag/AgCl), indicating diverse metabolic pathways likely support the observed electron uptake. Our work demonstrates culturing under various electrochemical and geochemical regimes allows for enhanced cultivation of diverse cathode-oxidizing microbes from one environmental system. Understanding the mechanisms of solid substrate oxidation from environmental microbes will further elucidation of the ecological relevance of these electron transfer interactions with implications for microbe-electrode technologies.

Isolation and Characterization of Human Gut Bacteria Capable of Extracellular Electron Transport by Electrochemical Techniques

Microorganisms are known to exhibit extracellular electron transfer (EET) in a wide variety of habitats. However, as for the human microbiome which significantly impacts our health, the role and importance of EET has not been widely investigated. In this study, we enriched and isolated the EET-capable bacteria from human gut microbes using an electrochemical enrichment method and examined whether the isolates couple EET with anaerobic respiration or fermentation. Upon the use of energy-rich or minimum media (with acetate or lactate) for electrochemical enrichment with the human gut sample at an electrode potential of +0.4 V [vs. the standard hydrogen electrode (SHE)], both culture conditions showed significant current production. However, EET-capable pure strains were enriched specifically with minimum media, and subsequent incubation using the δ-MnO2-agar plate with lactate or acetate led to the isolation of two EET-capable microbial strains, Gut-S1 and Gut-S2, having 99% of 16S rRNA gene sequence identity with Enterococcus avium (E. avium) and Klebsiella pneumoniae (K. pneumoniae), respectively. While the enrichment involved anaerobic respiration with acetate and lactate, further electrochemistry with E. avium and K. pneumoniae revealed that the glucose fermentation was also coupled with EET. These results indicate that EET couples not only with anaerobic respiration as found in environmental bacteria, but also with fermentation in the human gut.

Bulk Handling Facility Modeling and Simulation for Safeguards Analysis

The Separation and Safeguards Performance Model (SSPM) uses MATLAB/Simulink to provide a tool for safeguards analysis of bulk handling nuclear processing facilities. Models of aqueous and electrochemical reprocessing, enrichment, fuel fabrication, and molten salt reactor facilities have been developed to date. These models are used for designing the overall safeguards system, examining new safeguards approaches, virtually testing new measurement instrumentation, and analyzing diversion scenarios. The key metrics generated by the models include overall measurement uncertainty and detection probability for various material diversion or facility misuse scenarios. Safeguards modeling allows for rapid and cost-effective analysis for Safeguards by Design. The models are currently being used to explore alternative safeguards approaches, including more reliance on process monitoring data to reduce the need for destructive analysis that adds considerable burden to international safeguards. Machine learning techniques are being applied, but these techniques need large amounts of data for training and testing the algorithms. The SSPM can provide that training data. This paper will describe the SSPM and its use for applying both traditional nuclear material accountancy and newer machine learning options.

Facile Synthesis of Ordered Mesoporous Zirconia for Electrochemical Enrichment and Detection of Organophosphorus Pesticides

AbstractHighly crystallized mesoporous ZrO2 nanomaterials were synthesized by solvent evaporation induced self‐assembly approach. Ordered mesoporous ZrO2 nanomaterials were characterized by TEM, SEM, BET, XRD and UV‐Vis spectroscopy. The obtained nanomaterials exhibit the close‐packing mesopores with average pore size of 7 nm and a highly crystallized framework with tetragonal phase. A non‐enzyme electrochemical sensor based on ordered mesoporous ZrO2 is established for selective detection of methyl parathion (MP). The online extraction of MP is firstly achieved by ZrO2 modified electrode at open‐circuit potential for 5 min., and the sensitive detection of MP is performed by differential pulse voltammetry (DPV) method. By comparison, DPV responses of mesoporous ZrO2 are 40 times and 25 times larger than that of mesoporous silica and mesoporous carbon with the similar pore structure, implying the specific affinity advantage of zirconia to phosphoric group. The quantitative analysis result shows that the voltammetric currents are linear with concentrations of MP ranging from 1 ng/ml to 2 μg/ml with a detection limit of 0.53 ng/ml. The sensor also exhibits good stability and high selectivity against interfering species. The excellent analytical performances are owed to the accessible and uniform mesoporous structures, highly crystallized frameworks of ZrO2 and its specific affinity to phosphate groups.

Photoelectrochemical Stripping Analysis.

Electrochemical stripping analysis (ECSA) is a promising method for metal ions detection. However, the low sensitivity and poor reproducibility limits its practical applications. The combination with other powerful detection techniques to address these concerns is highly desirable. Herein, the anodic stripping method and photoelectrochemical (PEC) technique are integrated into a new detection platform of PEC stripping analysis (PECSA) with bismuth vanadate (BiVO4) as both optoelectronic material and an electrochemical enrichment candidate. The new PECSA strategy presents high sensitivity and excellent reproducibility; in addition, inherited from the ECSA, this strategy also offers new selectivity dimensions through the potential-dependent response and thus implements reproducible, sensitive, and selective detection of silver ion (Ag+) in real biological and environmental samples. The success of PECAS strategy shed light on the rational combination of various analysis techniques for versatile applications.