Catalytic reduction of hydrogen peroxide at metal hexacyanoferrate composite electrodes and applications in enzymatic analysis

The electrocatalytic activity of various metal hexacyanoferrates (Mhcfs) (i) immobilized on graphite electrodes, and (ii) as components of a composite electrode was investigated with respect to the reduction of hydrogen peroxide. The flow-through working electrode was a thin layer consisting of a composite of Mhcf, graphite, and polymethylmetacrylate (PMMA) as a binder, sandwiched between two Plexiglas plates. Among the pure Mhcfs immobilized on a graphite electrode, iron(III) hexacyanoferrate (Prussian blue) exhibits the highest electrocatalytic effect, whereas in the composite electrodes chromium(III) hexacyanoferrate (Crhcf) shows the highest activity and best performance and reproducibility for the electrochemical reduction of H₂O₂. The Crhcf electrode provides a linear dependence on H₂O₂ concentration in the range 2.5 × 10⁻⁶ mol L⁻¹ (LOD) to 1 × 10⁻⁴ mol L⁻¹ (phosphate buffer, pH 7). The sensor was applied for the detection of H₂O₂ enzymatically produced by glucose oxidase. The optimal conditions for the peroxide injection were 2 min after the beginning of the reaction and 25 °C with a detection limit of 7.0 × 10⁻⁶ mol L⁻¹ for glucose.     

Accelerated low water corrosion of carbon steel in the presence of a biofilm harbouring sulphate-reducing and sulphur-oxidising bacteria recovered from a marine sediment

Investigations were undertaken to elucidate causes of accelerated low water corrosion (ALWC) of steel piling in a harbour in Southern England. Visual inspection revealed features characteristic of ALWC such as the presence of poorly adherent, thick corrosion products of varying morphology, often seen as large blisters randomly located on sections of the structure at the low water mark. Upon the removal of blisters, a bright surface covered with shallow pits was exposed. Representative samples of the corrosion products were collected from the structure and water and sediment specimens were retrieved from selected areas in the harbour for microbiological, chemical and microscopy testing. In the laboratory, field samples were enriched to detect and enumerate communities of sulphur-oxidising bacteria (SOB) and sulphate-reducing bacteria (SRB). Biofilms, comprising SRB and SOB populations isolated from a sediment sample were grown under static conditions on surfaces of electrodes manufactured from steel piling material. Linear polarisation resistance (LPR) measurements revealed that the corrosion rate of steel with biofilms (0.518 mm y⁻¹) was higher than that recorded in sterile seawater alone (0.054 mm y⁻¹) and in sterile seawater to which nutrient was added (0.218 mm y⁻¹). Scanning electron microscopy (SEM) imaging demonstrated enhanced pitting under biofilms. The results of our investigation revealed for the first time that the attack on steel piling in the presence of sediment SRB and SOB populations was characteristic of ALWC.     

Determination of the kinetic parameters of oxygen reduction on copper using a rotating ring single crystal disk assembly (RRDCu(h k l)E)

The kinetics of the oxygen reduction reaction (orr) on Cu(h k l) surfaces are investigated in perchloric acid and sulfuric acid solutions using rotating ring disk electrode (RRD_Cu(h k l)E). Parameters, such as reaction order, kinetic current, rate constant, Tafel slopes as well as the number of electrons transferred are determined. The variation in the activity and reaction pathway with the crystal faces in different electrolytes is related to the surface characteristics of Cu(h k l) and the structure-sensitive inhibiting effect of the adsorbed anions on their surfaces. In 0.1 M HClO₄, the difference in activity is clearly observed on Cu(h k l) surfaces (Cu(1 0 0) > Cu(1 1 1) although it is relatively small). The higher activity of Cu(1 0 0) arises from its more open characteristics which may facilitate the co-adsorption of O₂. On the other hand, the adsorption of oxygenated species on Cu(1 1 1) at E > −0.35 V induces a 2 e⁻ pathway; while a 4 e⁻ reduction is observed on Cu(1 0 0) in the entire potential region (−0.70 V < E < −0.10 V). In 0.5 M H₂SO₄, the sequence in activity between Cu(1 1 1) and Cu(1 0 0) varies with the potentials, i.e., Cu(1 0 0) is initially more active than Cu(1 1 1) at −0.35 V < E < −0.15 V, however, the reversal in the activity between Cu(1 1 1) and Cu(1 0 0) is observed at more negative potentials (−0.45 V < E < −0.35 V). The desorption of strongly adsorbed (bi)sulfate anions on Cu(1 1 1) induces the 2 e⁻ reduction via peroxide formation, however, a 4 e⁻ reduction is dominant on the Cu(1 0 0) surfaces. The major effect of (bi)sulfate anions and oxygenated species on the orr kinetics and reaction pathway on Cu(h k l) surfaces is the blocking of active copper sites for the adsorption of O₂ molecules.     

Origin of the 2450 cm Raman bands in HOPG, single-wall and double-wall carbon nanotubes

The second order Raman signals around the G′-band region of graphite and carbon nanotubes have been investigated at more than 15 excitation laser lines. Two distinct Raman bands have been observed around 2700 cm⁻¹; a prominent one is due to the so-called G′-band and the other is a weak band around 2450 cm⁻¹. Both two bands can be from the double resonance process involving two phonons around the K-point in the phonon dispersion of a two-dimensional graphite. The 2450 cm⁻¹-band has exhibited little power dependence, whereas the intensity of G′-band has shown large photon energy dependence as already reported. The 2450 cm⁻¹-band and the G′-band correspond to non-dispersive q = 0 and fully-dispersive q = 2k, respectively. From the phonon dispersion and the corresponding phonon frequency, the 2450 cm⁻¹-band can be assigned as an overtone mode of LO phonon (i.e. 2LO). This is revealed by calculated Raman spectra of graphite with proper electron-phonon matrix elements. The present study is the first report on the origin and assignment of the 2450 cm⁻¹-band, which is based on the double resonance Raman scattering.     

Effects of phosphate species on localised corrosion of steel in NaHCO3 + NaCl electrolytes

Pitting corrosion of carbon steel electrodes in 0.1 M NaHCO₃ + 0.02 M NaCl solutions was induced by anodic polarisation. The evolution of the breakdown potential E_b with the phosphate concentration was investigated by linear voltammetry. E_b increased from −15 ± 5 mV/SCE for [HPO₄²⁻] = 0 to 180 ± 40 mV/SCE for [HPO₄²⁻] = 0.02 mol L⁻¹. During anodic polarisation (E = 50 mV/SCE), the behaviour of the whole electrode surface, followed by chronoamperometry, was compared to the behaviour of one single pit, followed via the scanning vibrating electrode technique (SVET). The addition of a Na₂HPO₄ solution after the beginning of the polarisation did not lead to the repassivation of pre-existing well-grown pits. The corrosion products forming in the pits were identified in situ by micro-Raman spectroscopy. They depended on the phosphate concentration. For [HPO₄²⁻] = 0.004 mol L⁻¹, siderite FeCO₃ was detected first. It was oxidised later into carbonated green rust GR(CO₃²⁻) by dissolved O₂. The beginning of the process is therefore similar to that observed in the absence of phosphate. Finally, GR(CO₃²⁻) was oxidised into ferrihydrite, the most poorly ordered form of Fe(III) oxides and oxyhydroxides. Phosphate species, adsorbing on the nuclei of FeOOH, inhibited their growth and crystallisation. For [HPO₄²⁻] = 0.02 mol L⁻¹, siderite was accompanied by an amorphous precursor of vivianite, Fe₂(PO₄)₃·8H₂O. This shows that, in any case, phosphate species interact strongly with the iron species produced by the dissolution of steel.     

An electrochemiluminescent biosensor for vitamin C based on inhibition of luminol electrochemiluminescence on graphite/poly(methylmethacrylate) composite electrode

A novel graphite/poly(methyl methacrylate) (graphite/PMMA) electrode was prepared in this paper. It was found that the developed polymer graphite paste electrode has some advantages in electrochemistry and electrochemiluminescence (ECL), such as high sensitivity, good reproducibility, quick and wide linear range of response to some biomolecules. The ECL behavior of luminol has been investigated in detail at the graphite/PMMA electrode, and vitamin C was found to be able to inhibit this ECL system. Based on which an inhibited ECL detection method has been developed for determination of vitamin C in this paper. The proposed method exhibited good reproducibility, wide-range linearity, high sensitivity and stability with a detection limit of 8.3 × 10⁻⁹ mol L⁻¹ (signal-to-noise ratio = 3) and linear response range of 2.5 × 10⁻⁸-1.0 × 10⁻⁴ mol L⁻¹. The relative standard deviation was 2.3% for 5 × 10⁻⁶ mol L⁻¹ vitamin C (n = 9). The possible mechanism for inhibition of luminol on graphite/PMMA electrode has also been proposed.     

Effects of NO2 ions on localised corrosion of steel in NaHCO3 + NaCl electrolytes

Pitting corrosion of carbon steel electrodes in 0.1 mol L⁻¹ NaHCO₃ + 0.02 mol L⁻¹ NaCl solutions was induced by anodic polarisation. The evolution of the breakdown potential E_b with NO₂⁻ concentration was investigated by linear voltammetry. E_b increased from −15 ± 5 mV/SCE for [NO₂⁻] = 0 up to 400 ± 50 mV/SCE for [NO₂⁻] = 0.1 mol L⁻¹. During anodic polarisation at potentials comprised between E_b([NO₂⁻] = 0) and E_b([NO₂⁻] ≠ 0), the behaviour of the whole electrode surface, followed by chronoamperometry, was compared to the behaviour of one single pit, followed via scanning vibrating electrode technique (SVET). Addition of a NaNO₂ solution after the beginning of the polarisation led to a rapid repassivation of pre-existing well-grown pits. In situ micro-Raman spectroscopy was then used to identify the corrosion products forming inside the pits. The first species to be detected in the presence of NO₂⁻ were mainly dissolved Fe(III) species, more likely [Fe^III(H₂O)₆]³⁺ complexes. Iron(II) carbonate FeCO₃, siderite, and carbonated green rust GR(CO₃²⁻) were also detected in the active pits, as in the absence of nitrite. But they were accompanied by maghemite γ-Fe₂O₃, a phase structurally similar to the passive film, that forms from the Fe(III) complexes. The Raman analyses then correlate with the SVET observations and confirm that the main effect of nitrite ions is to oxidize iron(II) into iron(III). The passive film would then form from the Fe(III) species still bound to the steel surface.     

Corrosion of carbon steel in sodium methanoate solutions

The behaviour of steel electrodes in sodium methanoate solutions was studied by coupling electrochemical techniques (voltammetry, OCP vs. time) with in situ micro-Raman spectroscopy analyses of the corrosion products. The polarisation curves depended strongly on the methanoate concentration. For the smallest concentration (10⁻³ mol L⁻¹), the current density increased regularly with the applied potential. So the behaviour of the electrode was typical of an active material. In contrast, for the largest concentration (10⁻¹ mol L⁻¹), the curves obtained were typical of a passive material. Methanoate ions favoured growth and stability of a passive oxide film more likely by adsorbing on its surface. The polarisation curve obtained for the intermediate concentration (10⁻² mol L⁻¹) was unusual and testified of an imperfect passivation of the steel surface. Finally, steel electrodes were left at the open circuit potential in the methanoate solutions. In any case, the passivity was rapidly lost and a general corrosion of the surface took place. In situ Raman spectroscopy analyses at the early stage of the corrosion process demonstrated that the first product to form was a green rust, GR(HCOO⁻). It was oxidised later into γ-FeOOH (lepidocrocite) by dissolved O₂. The process is then typical of what is usually observed in neutral or alkaline media, whatever the anions present and responsible of the GR formation. A new and detailed characterisation of GR(HCOO⁻) by X-ray diffraction was performed and a crystal structure is proposed.     

Inhibitory effect of non-ionic surfactants of the TRITON-X series on the corrosion of carbon steel in sulphuric acid

The corrosion inhibition characteristics of non-ionic surfactants of the TRITON-X series, known as TRITON-X-100 and TRITON-X-405, on stainless steel (SS) type X4Cr13 in sulphuric acid were investigated by potentiodynamic polarisation measurements. It was found that these surfactants act as good inhibitors of the corrosion of stainless steel in 2 mol L⁻¹ H₂SO₄ solution, but the inhibition efficiency strongly depends on the electrode potential. The polarisation data showed that the non-ionic surfactants used in this study acted as mixed-type inhibitors and adsorb on the stainless steel surface, in agreement with the Flory-Huggins adsorption isotherm. Calculated ΔG_ads values are −57.79 kJ mol⁻¹ for TRITON-X-100, and −87.5 kJ mol⁻¹ for TRITON-X-405. From the molecular structure it can be supposed that these surfactants adsorb on the metal surface through two lone pairs of electrons on the oxygen atoms of the hydrophilic head group, suggesting a chemisorption mechanism.     

Polypyrrole and La1−xSrxMnO3 (0≤ x ≤0.4) composite electrodes for electroreduction of oxygen in alkaline medium

Composite G/PPy/PPy(La_1−xSr_xMnO₃)/PPy electrodes made of the perovskite La_1−xSr_xMnO₃ embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La_1−xSr_xMnO₃) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm⁻³ pyrrole (Py) plus 0.05 mol dm⁻³ K₂SO₄ with and without containing a suspension of 8.33 g L⁻¹ oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm⁻³ K₂SO₄ plus 5 mmol dm⁻³ KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.     

Electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone/multi-walled carbon nanotubes immobilized on edge plane pyrolytic graphite electrode for NADH oxidation

This work reports the electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone (TCBQ)/multi-walled carbon nanotubes (MWCNT) immobilized on an edge plane pyrolytic graphite electrode for nicotinamide adenine dinucleotide (NADH) oxidation. Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) were used to confirms the presence of chloro after the nanotube modification with 2,3,5,6-tetrachloro-1,4-benzoquinone. The surface charge transfer constant, k_s, and the charge transfer coefficient for the modified electrode, α, were estimated as 98.5 (±0.6) s⁻¹ and 0.5, respectively. With this modified electrode the oxidation potential of the NADH was shifted about 300 mV toward a less positive value, presenting a peak current much higher than those measured on an unmodified edge plane pyrolytic graphite electrode (EPPG). Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the NADH oxidation reaction involves 2 electrons and a heterogenous rate constant (k_obs) of 3.1 × 10⁵ mol⁻¹ l s⁻¹. The detection limit, repeatability, long-term stability, time of response and linear response range were also investigated.     

Preparation of exfoliated graphite containing manganese oxides with high electrochemical capacitance by microwave irradiation

Exfoliated graphite (EG) containing manganese oxides was rapidly and efficiently prepared by microwave irradiation. The maximum expanded volume of EG was up to 317 mL g⁻¹ when the mass ratio of natural graphite and nitric acid to potassium permanganate was 1:2:2. EG showed specific capacitance of 97.5 F g⁻¹ at a scan rate of 1 mV s⁻¹ due to a pseudo-capacitance originated from the deposited manganese oxide particles on the surfaces of EG. After 400 cycles, the specific capacitance of EG increased by 21.2% of initial capacitance demonstrating good cycling stability.     

Impedance study of protecting film formation on lithium and lithiated graphite induced by bis(fluorosulfonyl) imide anion

The process of Li⁺ reduction from room temperature ionic liquids consisting of N-methyl-N-propylpyrrolidinium cation (MPPyr⁺) and bis(fluorosulfonyl) imide (FSI⁻) or bis(trifluoromethanesulfonyl) imide (TFSI⁻) anions was studied with the use of impedance spectroscopy. Reduction was carried out on both metallic lithium (Li) and graphite (G) electrodes. It has been found that the FSI anion in high amounts is able to form a protective film on both graphite and metallic lithium. The Li⁺/Li couple should rather be represented by a Li⁺/SEI/Li system. The SEI structure depends on the manner of its formation (chemical or electrochemical) and is not stable with time. The rate constant for the Li⁺ + e⁻ → Li process at the Li/SEI/Li⁺ (in MPPyrFSI) interface is k_o = 4.2 × 10⁻⁵ cm/s. In the case of carbon electrodes (G/SEI/Li⁺ interface), lithium diffusion in solid graphite is the rate determining step, reducing current by ca. two orders of magnitude, from ca. 10⁻⁴ A/cm², characteristic of the Li/SEI/Li⁺ electrode, to ca. 10⁻⁶ A/cm².     

Electrochemical insertion of sodium into graphite in molten sodium fluoride at 1025 °C

The electrochemical insertion of sodium into graphite was studied in molten sodium fluoride at 1025 °C. The results obtained evidenced two mechanisms for sodium insertion into graphite: sodium intercalation between the graphite layers and sodium sorption into the porosity of the material. Subsequent internal rearrangement of inserted sodium occurred, via transference from the pores towards the intercalation sites. In addition, the intercalation compound was found to undergo a fast decomposition process (k = 2.55 × 10⁻⁹ mol s⁻¹). X-ray diffraction analysis was used to confirm the formation of a high stage compound (Na_0.1C₈), the composition of which was consistent with compositions observed in the case of chemical vapor and electrochemical insertion of sodium, during experiments in the sodium perchlorate-ethylene cabonate electrolyte.     

An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et₄N⁺) and tetrafluoroborate (BF₄⁻) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et₄N⁺ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li⁺. For the positive electrode, BF₄⁻ was shown to intercalate above +4.3 V versus Li/Li⁺. The characteristic G-band doublet peak (E_2g2(i) (1578 cm⁻¹) and E_2g2(b) (1600 cm⁻¹)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm⁻¹) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm⁻¹) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).     

The influence of the synthesis conditions of graphite/tin nanoparticle materials on their electrode electrochemical performance in Li-ion battery anodes

Electrochemical lithium insertion was carried out in tin-graphite composites obtained by two different preparation processes. In the first graphite was mixed with the products obtained by reduction of SnCl₄ with Na tert-Butanoate (t-BuONa)-activated NaH (two-step synthesis). The second used materials synthesized by reducing SnCl₄ with a graphite and (t-BuONa)-activated NaH suspension in THF (one-pot synthesis). Both composites were characterized by X-ray diffraction and transmission electron microscopy . It appeared that the tin particle size was controlled by the reduction time of SnCl₄. The stability of the electrochemical capacity of composites prepared by the two-step synthesis is dependent on the tin particle size: a stable capacity upon cycling was shown with subnanometer particles while a capacity fade was observed with larger nanoparticles. In materials prepared by the one pot synthesis, tin was present either as nanopartcles supported on graphite or as free aggregates. An initial reversible capacity of 630 mA hg⁻¹ decayed to a constant value of 415 mA hg⁻¹ after 12 charge/discharge cycles. It was hypothesized that the fraction of tin bound to graphite contributed to the stable reversible capacity while free tin aggregates were responsible for its decay.     

Determination of the step dipole moment and the step line tension on Ag(0 0 1) electrodes

Using impedance spectroscopy, we determined the step dipole moment and the potential dependence of the step line tension of silver electrodes in contact with an electrolyte: (0 0 1) and vicinal surfaces (1 1 n) with n = 5, 7, 11 in 10 mM ClO₄⁻-solutions were investigated. The step dipole moment is determined from the shift of the potential of zero charge (pzc) as a function of the surface step density. The dipole moment per step atom was found to be 3.5 ± 0.5 × 10⁻³ e Å. From the pzc and the potential dependence of the capacitance curves, the potential dependence of the surface tension of the vicinal surfaces is determined. The line tension of the steps is then calculated from the difference between the surface tensions of stepped (1 1 n) and the nominally step-free (0 0 1) surfaces. The results are compared to a previous study on Au(1 1 n) surfaces. For gold, the step line tension decreases roughly linear with potential, whereas a parabolic shape is observed for silver.     

Microbial electrocatalysis with Geobacter sulfurreducens biofilm on stainless steel cathodes

Stainless steel and graphite electrodes were individually addressed and polarized at −0.60 V vs. Ag/AgCl in reactors filled with a growth medium that contained 25 mM fumarate as the electron acceptor and no electron donor, in order to force the microbial cells to use the electrode as electron source. When the reactor was inoculated with Geobacter sulfurreducens, the current increased and stabilized at average values around 0.75 A m⁻² for graphite and 20.5 A m⁻² for stainless steel. Cyclic voltammetry performed at the end of the experiment indicated that the reduction started at around −0.30 V vs. Ag/AgCl on stainless steel. Removing the biofilm formed on the electrode surface made the current totally disappear, confirming that the G.sulfurreducens biofilm was fully responsible for the electrocatalysis of fumarate reduction. Similar current densities were recorded when the electrodes were polarized after being kept in open circuit for several days. The reasons for the bacteria presence and survival on non-connected stainless steel coupons were discussed. Chronoamperometry experiments performed at different potential values suggested that the biofilm-driven catalysis was controlled by electrochemical kinetics. The high current density obtained, quite close to the redox potential of the fumarate/succinate couple, presents stainless steel as a remarkable material to support biocathodes.     

Hydrated Mn(IV) oxide-exfoliated graphite composites for electrochemical capacitor

Commercially available low cost exfoliated graphite (EG, nominal diameter 130 μm) was used as a conductive substrate for electrochemical capacitor of hydrated Mn(IV) oxide, MnO₂·nH₂O. The MnO₂·nH₂O-EG composites were prepared by addition of EG to potassium permanganate solution, followed by 1 h stirring and then slow addition of manganese(II) acetate solution. By this procedure submicrometer or smaller sized MnO₂·nH₂O particles having mesopores of 6-12 nm in diameter were formed on the graphite sheets of EG. Although EG alone showed only about 2 F g⁻¹, the composites showed good rectangular cyclic voltammograms at 2-20 mV s⁻¹ in 1 mol L⁻¹ Na₂SO₄. The capacitance per net amount of MnO₂ increased proportionally with EG content, that is, utilization ratio of MnO₂ increased with EG content. The composites of MnO₂·nH₂O and smaller diameter of EG (nominal diameter 45 μm) or artificial graphite powder (average diameter 3.7 μm) showed fairly good performance at 2 mV s⁻¹, but with increasing potential scan rate the rectangular shape was distorted and capacitance decreased drastically. The results implies that sheet-like structure is more effective than small particles as conductive materials, when the formation procedure of composite is the same. Large sized EG may be a promising conductive material for electrochemical capacitors.     

Characterizations of expanded graphite/polymer composites prepared by in situ polymerization

Poly(styrene-co-acrylonitrile)/expanded graphite composite sheets with very low in-plane (8.5 × 10⁻³ Ω cm) and through-thickness (1.2 × 10⁻² Ω cm) electrical resistivities have been prepared. The expanded graphite was made by oxidation of natural graphite flakes, followed by thermal expansion at 600 °C. Microscopic results disclosed that the expanded graphite has a legume-like structure, and each “legume” has a honeycomb sub-structure with many diamond-shaped pores. After soaking the expanded graphite with styrene and acrylonitrile monomers, the polymer/expanded graphite composite granules were obtained by in situ polymerization of the monomers inside the pores at 80 °C. The functional groups and microstructures of the oxidized graphite, expanded graphite and composites in the forms of particles or sheets were carefully characterized using various techniques, including X-ray powder diffraction, thermogravimetry, optical and electron microscopy. It was found that the honeycomb sub-structure survived after hot-pressing, resulting in a graphite network penetrating through the entire composite body, which produces a composite with excellent electrical conductivity.