Antifouling Membranes Research Articles

Reinforcing hydration layer on membrane surface via nano-capturing and hydrothermal crosslinking for fouling reduction

Polyvinylidene fluoride (PVDF)@Fe3O4 composite membranes were prepared by phase inversion, followed by crosslinking with hydrophilic silane-based prepolymers. The influences of Fe3O4 nanoparticles (NPs) on morphology, chemistry, hydrophilicity, electric charge and roughness of membrane surfaces were investigated by a number of characterization techniques. The results revealed that the dispersed Fe3O4 nanoparticles reduced the micropores of the composite membrane and maintained the membrane surface roughness. Meanwhile, the dispersed Fe3O4 enabled the membrane to capture more hydrophilic silane-based prepolymers, thereby leading to a robust, dense and zwitterionic characteristic hydration layer on the membrane surface. The reinforced hydration layer imparted the membrane surface with more stable water permeability and higher rejections to humic acid (HA), bovine serum albumin (BSA) and soybean oil during five cycles of cross-flow separation. According to the resistance-in-series model, the anti-oil-fouling mechanism of the membrane relied on manipulating the hydration layer on the membrane surface to prevent the foulants from approaching the membrane surface. The surface-immobilized Fe3O4 facilitated the hydration layer to repel HA and BSA to permeate through the membrane via chelation and adsorption, and then reduced the membrane internal fouling. Our findings provide a new strategy to construct antifouling membrane surfaces by properly tailoring the strength and thickness of the surface hydration layer.

Influence of Preparation Temperature on the Properties and Performance of Composite PVDF-TiO2 Membranes.

Composite PVDF-TiO2 membranes are studied extensively in literature as effective anti-fouling membranes with photocatalytic properties. Yet, a full understanding of how preparation parameters affect the final membrane structure, properties and performance has not been realized. In this study, PVDF-TiO2 membranes (20 wt% TiO2/PVDF) were fabricated via the non-solvent-induced phase separation (NIPS) method with an emphasis on the preparation temperature. Then, a systematic approach was employed to study the evolution of the membrane formation process and membrane properties when the preparation temperature changed, as well as to establish a link between them. Typical asymmetric membranes with a high porosity were obtained, along with a vast improvement in the permeate flux compared to the neat PVDF membranes, but a reduction in mechanical strength was also observed. Interestingly, upon the increase in preparation temperature, a significant transition in membrane morphology was observed, notably the gradual diminution of the finger-like macrovoids. Other membrane properties such as permeability, porosity, thermal and mechanical properties, and compression behavior were also influenced accordingly. Together, the establishment of the ternary phase diagrams, the study of solvent–nonsolvent exchange rate, and the direct microscopic observation of membrane formation during phase separation, helped explain such evolution in membrane properties.

Molecular grafting and zwitterionization based antifouling and underwater superoleophobic PVDF membranes for oil/water separation

Effective surface modification strategies are at the core of developing efficient and antifouling membranes for a range of separation, purification, and wastewater treatment applications. The inherently hydrophobic nature of most polymeric membranes is one of the primary factors for their high fouling susceptibility. In this work, we have designed a simple and straightforward membrane modification methodology utilizing the reactive nature of polydopamine to molecularly graft short chain amino alkanes followed by zwitterionization using 1,3-propanesultone. The prepared membranes demonstrated superhydrophilicity accompanied with underwater superoleophobicity originating from the hydrophilic nature of polydopamine, aminoalkanes, and strong hydration due to zwitterionic functionality. The surface chemistry, nanostructuring, and surface roughness play an essential role in delivering required properties in the membranes. The prepared membranes showed ultrahigh BSA protein resistance and low oil droplets adhesion. The functionalized membranes showed a manifold boost in permeability for pure water and BSA solution, and separation of oil-water emulsion at high permeation rates. The antifouling nature of the membranes helped in maintaining the permeation behavior for multiple cycles with >96% flux recovery after ten consecutive cycles and excellent rejection in oil-water emulsion separation (>98%). The superwetting properties, along with high permeation, rejection, and antifouling properties, make these membranes a potential candidate for oily water separation and demonstrate the effectiveness of simple molecular level grafting and functionalization as a straightforward method for membrane modifications.

Hydrophilic and underwater superoleophobic porous graphitic carbon nitride (g-C3N4) membranes with photo-Fenton self-cleaning ability for efficient oil/water separation

Due to the great fouling resistance property, (super)hydrophilic/underwater superoleophobic membranes are prevalent candidates for oil-polluted wastewater treatment. Even so, membrane fouling inevitably occurs during long-term operation. Therefore, it is of great significance to construct anti-fouling membranes with robust flux recovery. Herein, a polyvinyl pyrrolidone (PVP) coated porous potassium-doped g-C3N4 (PKCN) membrane was fabricated for the first time by vacuum filtration. The as-prepared membrane displays enhanced hydrophilicity and underwater superoleophobicity. The permeability of the membrane increased significantly after sonication treatment, which is attributed to the increased pore volume and small nanosheets size that shorten the transport pathway of water molecules. Importantly, owing to the high photo-Fenton activity, the PKCN membrane exhibits fast (within 15 min) and excellent flux recovery (96.5%) after the photo-Fenton cleaning process. Furthermore, after 10 repeated usages, the PKCN membrane still keeps stable permeability and excellent purification efficiency. This work opens a door for developing self-cleaning membranes with the superior anti-fouling ability for effective oil/water separation.

Antifouling Fibrous Membrane Enables High Efficiency and High-Flux Microfiltration for Water Treatment.

Membrane biofouling has long been a major obstacle to highly efficient water treatment. The modification of the membrane surface with hydrophilic materials can effectively enhance biofouling resistance. However, the water flux of the membranes is often compromised for the improvement of antifouling properties. In this work, a composite membrane composed of a zwitterionic hydrogel and electrospinning fibers was prepared by a spin-coating and UV cross-linking process. At the optimum conditions, the composite membrane could effectively resist the biofouling contaminations, as well as purify polluted water containing bacteria or diatoms with a high flux (1349.2 ± 85.5 L m-2 h-1 for 106 CFU mL-1 of an Escherichia coli solution). Moreover, compared with the commercial poly(ether sulfone) (PES) membrane, the membrane displayed an outstanding long-term filtration performance with a lower water flux decline. Therefore, findings in this work provide an effective antifouling modification strategy for microfiltration membranes and hold great potential for developing antifouling membranes for water treatment.

Bimetallic polyphenol networks structure modified polyethersulfone membrane with hydrophilic and anti-fouling properties based on reverse thermally induced phase separation method

In order to improve the hydrophobicity of traditional polyethersulfone (PES) membranes, this study combined the reverse thermally induced phase separation (RTIPS) method with the constructed bimetallic polyphenol networks (BMPNs) to prepare hydrophilic anti-fouling membranes. As for BMPNs, tannic acid (TA) was served as an intermediate to construct both the inner and surface hydrophilic layers of the PES membranes. On the one hand, etching Zeolitic imidazolate framework-8 (EZIF-8) with synergistic etching and surface functionalization via TA not only retained the high pore structure of MOFs, but also had good hydrophilicity. On the other hand, the MPN hydrophilic layer was formed on the membrane surface by the combination of TA from the surface of EZIF-8 and iron ions in the coagulation bath. Therefore, BMPNs structure penetrated the interior and surface of PES membrane, which greatly improved the hydrophilic properties. In addition, the membrane with porous surfaces and spongy cross sections by RTIPS method improved the permeability and mechanical properties of the membrane by several times compared with the membrane via NIPS method. The obtained membranes in this experiment showed excellent permeability, just like pure water flux reached 1662.16 L/m2 h, while BSA rejection rate remained at 92.78%. Compared with pure membrane, it showed a better flux recovery rate (FRR = 83.33%) after cleaning, and the reduction of irreversible (Rir = 16.67%) fouling indexes indicated that the adsorption of protein was inhibited. These results suggested that the hydrophilic anti-fouling PES membranes prepared by this method possessed great application potential in membrane separation technology.

Mechanically strong Janus tri-bore hollow fiber membranes with asymmetric pores for anti-wetting and anti-fouling membrane distillation

Wetting, fouling and mechanical robustness are three major challenges constraining the commercial applications of membrane distillation (MD). Herein, we have developed a robust Janus tri-bore hollow fiber membrane with anti-wetting/fouling resistance. The unique membrane was fabricated by an oxidant-induced deposition of polydopamine/polyethylenimine (PDA/PEI) and a subsequent grafting of sodium-functionalized carbon quantum dots (Na+-CQDs) on top of a hydrophobic tri-bore polyvinylidene fluoride (PVDF) hollow fiber membrane. The PDA/PEI deposition resulted in a nanoporous top layer, and the Na+-CQD grafting significantly enhanced the membrane surface hydrophilicity. In MD operations, the nanoporous PDA/PEI layer endowed the membrane with an excellent rejection to surfactants, thus reducing the wetting propensity, while the grafted Na+-CQDs facilitated the formation of a surface hydration layer, thereby mitigating the oil fouling. This study may expand the applications of mechanically robust tri-bore MD hollow fiber membranes to desalinate hypersaline and harsh wastewaters containing amphiphilic and hydrophobic contaminants.

Progress in Research and Application of Nanofiltration (NF) Technology for Brackish Water Treatment.

Brackish water is a potential fresh water resource with lower salt content than seawater. Desalination of brackish water is an important option to alleviate the prevalent water crisis around the world. As a membrane technology ranging between UF and RO, NF can achieve the partial desalination via size exclusion and charge exclusion. So, it has been widely concerned and applied in treatment of brackish water during the past several decades. Hereon, an overview of the progress in research on and application of NF technology for brackish water treatment is provided. On the basis of expounding the features of brackish water, the factors affecting NF efficiency, including the feed water characteristics, operating conditions and NF membrane properties, are analyzed. For the ubiquitous membrane fouling problem, three preventive fouling control strategies including feed water pretreatment, optimization of operating conditions and selection of anti-fouling membranes are summarized. In addition, membrane cleaning methods for restoring the fouled membrane are discussed. Furthermore, the combined utilization of NF with other membrane technologies is reviewed. Finally, future research prospects are proposed to deal with the current existing problems. Lessons gained from this review are expected to promote the sustainable development of brackish water treatment with NF technology.

Advances in the Synthesis and Application of Anti-Fouling Membranes Using Two-Dimensional Nanomaterials.

This article provides a comprehensive review of the recent progress in the application of advanced two-dimensional nanomaterials (2DNMs) in membranes fabrication and application for water purification. The membranes fouling, its types, and anti-fouling mechanisms of different 2DNMs containing membrane systems are also discussed. The developments in membrane synthesis and modification using 2DNMs, especially graphene and graphene family materials, carbon nanotubes (CNTs), MXenes, and others are critically reviewed. Further, the application potential of next-generation 2DNMs-based membranes in water/wastewater treatment systems is surveyed. Finally, the current problems and future opportunities of applying 2DNMs for anti-fouling membranes are also debated.

Electrostatic enhanced surface segregation approach to self-cleaning and antifouling membranes for efficient molecular separation

Membranes with excellent antifouling properties and persistent high permeance are eternal pursuits in membrane technology. Herein, we proposed an electrostatic enhanced surface segregation approach toward the antifouling and self-cleaning membranes for molecular separation. A copolymer containing quaternary ammonium (QA) segments was designed as the surface segregation agent in the casting solution, while polysulphonic acid (PSA) was designed as the crosslinking agent in the coagulation bath. Driven by the electrostatic interactions between the positively charged QA and negatively charged sulphonic groups, the copolymer and PSA were in-situ assembled during the non-solvent induced phase separation (NIPS) processes, generating a selective separation layer on the polymeric matrix. The segregation of copolymer was enhanced, leading to a high surface coverage of ionic QA and sulphonic groups and a significantly improved surface hydrophilicity. Accordingly, the membrane exhibited a high water permeance up to 124 Lm−2h−1bar−1 with dye rejection over 95%. Moreover, the membrane exhibited excellent antifouling performance with the ultralow total permeance decline of 1.2% and the ultrahigh permeance recovery ratio of 99.8% against emulsified oil, as well as the self-cleaning property against crude oil. Hopefully, this study can afford a novel and generic approach to antifouling and self-cleaning membranes for diverse separations.

Enhancement of the photocurrent and electrochemical properties of the modified nanohybrid composite membrane of cellulose/graphene oxide with magnesium oxide nanoparticle (GO@CMC.MgO) for photocatalytic antifouling and supercapacitors applications

A novel nanohybrid material (NHM) of magnesium oxide nanoparticle (MgO NPs) and modified antifouling membrane surface of graphene oxide nanosheet (GO) and carboxymethylcellulose (CMC) has been created via precipitation and ultrasonication methods, then characterized via various techniques for a novel antifouling membrane for water treatment, and supercapacitor applications for energy applications. The electrochemical properties of nanohybrid material (NHM) have been synthesized successfully by the cyclic voltammetry technique for detecting charge transfer, supercapacitor, and energy storage. Also, the optical properties of NHM antifouling nanomembrane have been detected by zeta potential and UV-spectroscopy apparatus for the following the generation of electrons, charge transfer, and formation of the reactive oxygen species (ROS) for oxidation of the organic materials pollutants for water treatment. The electron transfer of GO@CMC.MgO has been revealed via the photocatalytic process for the degradation of organic and inorganic pollutions. The supercapacitor and energy applications have been detected via the measurements of electrochemical impedance spectroscopy (EIS) by Nyquist plots, the following results have been obtained:-A good electron transfer has been detected with GO@CMC.MgO NHM.-The photocatalytic process with organic compounds pollution has been detected.-The supercapacitor and energy application have been revealed.The Results demonstrated that the fabricated NHM is promising electrode material for supercapacitor applications, energy storage and water treatment.

Surface modification of nanofiltration membranes with zwitterions to enhance antifouling properties during brackish water treatment: A new concept of a “buffer layer”

Nanofiltration (NF)-based brackish water desalination has been labeled an emerging avenue for alleviating water scarcity, however, membrane fouling still restricts its broad application. Herein, zwitterion-modified membranes were prepared with polydopamine (PDA) and sulfobetaine methacrylate (SBMA) monomers via surface-initiated atom-transfer radical-polymerization (SI-ATRP) and named TFC-PDA-PSBMA. Compared with the control membrane, the TFC-PDA-PSBMA possessed enhanced hydrophilicity, lower negative charge and smaller pore size. Superior salt retention of Na2SO4 and NaCl of up to 99.1% and 80.7% was obtained for TFC-PDA-PSBMA with only a 10% decrease in permeance. Furthermore, TFC-PDA-PSBMA exhibited an outstanding flux recovery of 92.1% during humic acid (HA) filtration. The mechanism driving the improved antifouling properties was analyzed from the aspects of the modified layer, free interfacial energy and hydration layer. TFC-PDA-PSBMA also exhibited superior antibiofouling with reducing 86.1% of E. coli colonies adhered on membrane surface. The SBMA layer and hydration layer acted together as a buffer layer with robust repulsion of foulants. In addition, the TFC-PDA-PSBMA membrane was applied in authentic brackish water desalination and exhibited superior selectivity, desalination and antifouling performance, which matched the simulated solution results well. A new concept of a “buffer layer” was proposed in this work, which may provide insight into antifouling membrane design during brackish water treatment.

Photocatalytic GO/M88A “interceptor plate” assembled nanofibrous membrane with photo-Fenton self-cleaning performance for oil/water emulsion separation

Developing the high-efficient and robust antifouling membranes for oily emulsions to achieve the purpose of prolonging the service life of the membrane shows great demand because of the restriction of hydration anti-fouling mechanism strategy to against pollution. Herein, a hydrophilic photo-Fenton-like catalyst – GO/Fe-MOF assembled stabilized polyacrylonitrile (SPAN) nanofibrous membrane with underwater superoleophobicity, robust mechanical strength and photo-Fenton self-cleaning performance was firstly designed and fabricated via ultrasonic assistance, mussel-inspired fixation and low temperature hydrothermal synthesis methods. In this work, benefiting by the regulable amounts of GO nanosheets on the SPAN@GO/M88A membrane surface, the obtained membrane possessed sub-micrometer skin layer, which guarantees the balance of fast permeation flux (920–7083 ± 47 L m−2 h−1) and separation efficiency (>99.2%) for diesel/water emulsion with small emulsified oils. Moreover, introduced hydrophilic Metal-organic frame nanoparticles (MIL-88A (Fe)) into modified membrane endowed underwater anti-oil-fouling and photo-Fenton catalytic degradation performance for organic contaminants. Meanwhile, the charged GO/M88A heterostructure can assist to achieve demulsification for separation of surfactant-stabilized emulsions by strong electrostatic force. More importantly, attached and irremovable contaminants on the membrane can be quickly removed by photo-Fenton self-cleaning method, and achieved over 96% of recovery flux recovery ratio, which effectively prolonged the service life of the membrane. We believe the newly designed SPAN@GO/M88A membrane with hydration antifouling and photo-Fenton self-cleaning properties can stimulate more studies on revivable separation membranes for multifunctional applications.

Effect of various operating parameters towards PVDF/HMO mixed matrix membrane performance

The development of antifouling membranes to separate oil/water emulsions in various environmental approaches is urgently needed. This work reports on the development of a mixed matrix membrane (MMM) using polyvinylidene fluoride (PVDF) incorporated with self-synthesized hydrous manganese oxide (HMO). The filtration performance was compared to the pristine PVDF membrane in terms of flux and rejection efficiency. The membranes were characterized and evaluated under various operating parameters: different oil/water emulsion feed concentrations (50, 100, 500, and 1000 ppm), cycle stability, long-term membrane stability, and flux recovery ratio (FRR). When tested with a 1000 ppm oil/water emulsion feed concentration, the fabricated MMM exhibited higher flux performance of approximately eight folds compared to the pristine membrane, with the FRRs of 87% and 56%, respectively. After the eighth cycle, the performance of the MMM decreased gradually. However, the pristine membrane had completely collapsed at the end of the recyclability test. Furthermore, the modified PVDF/HMO MMM was physically stable for up to 6 h during the long-term stability study, indicating the potential of HMO in improving separation performance and the lifespan of MMM.

In situ engineering of an ultrathin polyamphoteric layer on polyketone-based thin film composite forward osmosis membrane for comprehensive anti-fouling performance

Thin film composite (TFC) membranes easily suffer from fouling induced by oil and other pollutants during forward osmosis (FO) due to the relatively hydrophobic chemistry and rough structure of polyamide (PA). To achieve comprehensive anti-fouling properties, poly(2-methacryloyloxyethyl phosphorylcholine-co-2-aminoethyl methacrylate hydrochloride) (MPC-co-AEMA) was immobilized on top of a polyketone (PK)-based TFC membrane following a single-step simultaneous deposition with dopamine. The adhesive properties of polydopamine (PDA), as well as the covalent interactions between PDA and MPC-co-AEMA, ensured the firm immobilization of the MPC-co-AEMA on PA layer. As a result of the simultaneous deposition of PDA and MPC-co-AEMA, a high-performance and superhydrophilic and underwater superoleophobic TFC membrane was engineered. In addition, the outstanding water adsorption capacity of the polyamphoteric layer resulted in better protein adhesion mitigation. FO operation using various foulants also demonstrated a high fouling resistance of the PK-TFC-PDA/MPC membrane, especially during the treatment of wastewater emulsion containing high concentration of oil and bovine serum albumin (BSA). In summary, the findings in this study could provide insights into the preparation of anti-fouling membranes for wastewater purification using FO.

Amphiphilic antifouling membranes by polydopamine mediated molecular grafting for water purification and oil/water separation

A polydopamine mediated amphiphilic molecular grafting approach was designed by combining hydrophilic and hydrophobic segments into the same moiety for creating amphiphilic surfaces with enhanced antifouling properties. Polydopamine (PDA) coating was performed on microporous polysulfone (PSF) membranes to form an active mediating layer. After that N,N-dimethyl ethylenediamine (DMEDA) was grafted on the PDA layer via Michael addition reaction and the tertiary amine functionality of DMEDA was reacted with 1-Iodo-1H,1H,2H, 2H-perfluorodecane to obtain amphiphilic molecular functionalization. All modification steps were confirmed by characterizations using X-ray photoelectron spectroscopy, scanning electron microscopy, capillary flow porometry, and surface wetting using a dynamic contact angle method. The antifouling study by protein adsorption shows that the hydrophilic-hydrophobic molecular layers in proximity effectively prevent nonspecific protein adsorption compared to the virgin PSF membrane. The antifouling property was further evaluated by real-time cyclic filtration with a 5 mg ml−1 bovine serum albumin (BSA) solution. The final modified amphiphilic surface has shown reduced irreversible protein bounded properties on and inside the membrane surfaces along with high flux recovery. Furthermore, the oil-in-water emulsion filtration shows excellent oil rejection at a high flux rate with nearly complete flux recovery. These findings indicate a promising and smart membrane surface modification technique that can be readily tailored for water filtration and separation applications.

Enhancing the antifouling property of polymeric membrane via surface charge regulation

In this study, positively charged monomers were grafted onto negatively charged membranes via UV radiation to improve the antifouling/antibiofouling properties of the polymeric membrane and the stability of the modification layer. The surface properties, morphologies, antifouling and antibiofouling properties, and stability of the modified membranes were systematically characterized. Results indicated that the introduction of [2-(methacryloyloxy) ethyl] trimethylammonium chloride (MTAC) monomers onto polyethersulfone (PES)/sulfonated polyethersulfone (SPES) membranes effectively increased the surface hydrophilicity. Meanwhile, the surfaces were neutralized with ~0 mV zeta potential in pH 3–10. Moreover, the formation of a polyampholytic copolymer and the antibacterial ability of MTAC considerably improved the antibiofouling properties of the modified membranes. The MTAC-grafted PES/SPES membranes showed excellent antifouling/antibiofouling properties during the treatment of various types of wastewater, including bovine serum albumin solution, oil/water emulsion, and bacterial suspension. Therefore, this study provides a simple and effective method of constructing stable and antifouling membranes for sustainable water treatment.

New Insights into the Microbial Diversity of Cake Layer in Yttria Composite Ceramic Tubular Membrane in an Anaerobic Membrane Bioreactor (AnMBR).

Cake layer formation is an inevitable challenge in membrane bioreactor (MBR) operation. The investigations on the cake layer microbial community are essential to control biofouling. This work studied the bacterial and archaeal communities in the cake layer, the anaerobic sludge, and the membrane cleaning solutions of anaerobic membrane bioreactor (AnMBR) with yttria-based ceramic tubular membrane by polymerase chain reaction (PCR) amplification of 16S rRNA genes. The cake layer resistance was 69% of the total membrane resistance. Proteins and soluble microbial by-products (SMPs) were the dominant foulants in the cake layer. The pioneering archaeal and bacteria in the cake layer were mostly similar to those in the anaerobic bulk sludge. The dominant biofouling bacteria were Proteobacteria, Bacteroidetes, Firmicutes, and Chloroflexi and the dominant archaeal were Methanosaetacea and Methanobacteriacea at family level. This finding may help to develop antifouling membranes for AnMBR treating domestic wastewater.

A biomimetic antimicrobial surface for membrane fouling control in reverse osmosis for seawater desalination

Membrane fouling occurs in all membrane processes. Surface modifications have gained popularity for enhancing membrane antifouling capability via introducing a hydrophilic component or reducing membrane surface roughness. In this work, we proposed to develop a green antimicrobial lysozyme nanofilm on the polyamide membrane surface with remarkable antibacterial and antifouling properties to effectively reduce membrane fouling. The nanofilm is rooted in the molecular assembly of a protein which is an extraction of food and natural products. The nanofilm exhibits the combination of various functions including antimicrobial, antifouling and antibiofilm. This protein-based nanofilm is robustly transferred and self-adhered on the membrane surface by a simple one-step aqueous coating. The modified RO membrane exhibited good performance in bacterial reduction of ~50% in comparison to the control membrane and experienced almost zero loss in water flux and salt rejection under SWRO testing condition. The membrane is further evaluated with real seawater for 14 days and the modified membrane showed its superiority in flux and fouling control which were verified by the confocal laser scanning microscopy (CLSM) and quantified by inductively coupled plasma optical emission spectrometer (ICP-OES). This work demonstrates that the protein-based biomaterials offer a safe and environmentally friendly way of antimicrobials, which can reduce membrane fouling significantly in membrane filtration.

An electrochemical sensor based on an anti-fouling membrane for the determination of histamine in fish samples.

Electrochemical determination of histamine (HA) is quite challenging owing to the high oxidation potential and electrode fouling from HA oxide polyhistamine, which leads to poor sensitivity and unrepeatable measurement. In the present work, a simple, sensitive and repeatable electrochemical measurement of HA was developed based on a Nafion and multi-walled carbon nanotube (MWCNTs) composite membrane modified glassy carbon electrode (GCE). Compared with the bare GCE, the Nafion and MWCNT composite membrane modified electrode significantly enhanced the oxidation peak current and reduced the peak potential to 1.12 V (vs. SCE). Moreover, the characterization of the modified electrode by XPS and EIS showed that polyhistamine scarcely deposited on the composite membrane of the modified GCE, which made it possible to realize repeatable electrochemical measurement of HA. The electrochemical oxidation behavior of HA on the modified electrode was studied by differential pulse voltammetry (DPV). The oxidation peak current has linear and natural log-linear relationships with HA concentration in the range of 20-200 μmol L-1 and 0.5-10 μmol L-1, respectively. The detection limit was 0.39 μmol L-1 (S/N = 3). The modified electrode could be used to determine 100 μmol L-1 HA ten times repeatedly; the peak currents in consecutive runs were all above 95% of the initial response. This method was also successfully applied to the determination of HA in fish samples and recoveries ranged from 98.2 to 101.2%.