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1.
There is great interest in hydrogen evolution in bioelectrochemical systems, such as microbial electrolysis cells (MECs), but these systems require non-optimal near-neutral pH conditions and the use of low-cost, non-precious metal catalysts. Here we show that molybdenum disulfide (MoS2) composite cathodes have electrochemical performance superior to stainless steel (SS) (currently the most promising low-cost, non-precious metal MEC catalyst) or Pt-based cathodes in phosphate or perchlorate electrolytes, yet they cost ∼4.5 times less than Pt-based composite cathodes. At current densities typical of many MECs (2-5 A/m2), the optimal surface density with MoS2 particles on carbon cloth was 25 g/m2, achieving 31 mV less hydrogen evolution overpotential than similarly constructed Pt cathodes in galvanostatic tests with a phosphate buffer. At higher current densities (8-10 A/m2) the MoS2 catalyst had 82 mV less hydrogen evolution overpotential than the Pt-based catalyst. MoS2 composite cathodes performed similarly to Pt cathodes in terms of current densities, hydrogen production rates and COD removal over several batch cycles in MEC reactors. These results show that MoS2 can be used to substantially reduce the cost of cathodes used in MECs for hydrogen gas production.  相似文献   

2.
Microbial fuel (MFCs) and electrolysis cells (MECs) can be used to recover energy directly as electricity or hydrogen from organic matter. Organic removal efficiencies and values of the different energy products were compared for MFCs and MECs fed winery or domestic wastewater. TCOD removal (%) and energy recoveries (kWh/kg-COD) were higher for MFCs than MECs with both wastewaters. At a cost of $4.51/kg-H2 for winery wastewater and $3.01/kg-H2 for domestic wastewater, the hydrogen produced using MECs cost less than the estimated merchant value of hydrogen ($6/kg-H2). 16S rRNA clone libraries indicated the predominance of Geobacter species in anodic microbial communities in MECs for both wastewaters, suggesting low current densities were the result of substrate limitations. The results of this study show that energy recovery and organic removal from wastewater are more effective with MFCs than MECs, but that hydrogen production from wastewater fed MECs can be cost effective.  相似文献   

3.
Although platinum is commonly used as catalyst on the cathode in microbial electrolysis cells (MEC), non-precious metal alternatives are needed to reduce costs. Cathodes were constructed using a nickel powder (0.5–1 μm) and their performance was compared to conventional electrodes containing Pt (0.002 μm) in MECs and electrochemical tests. The MEC performance in terms of coulombic efficiency, cathodic, hydrogen and energy recoveries were similar using Ni or Pt cathodes, although the maximum hydrogen production rate (Q) was slightly lower for Ni (Q = 1.2–1.3 m3 H2/m3/d; 0.6 V applied) than Pt (1.6 m3 H2/m3/d). Nickel dissolution was minimized by replacing medium in the reactor under anoxic conditions. The stability of the Ni particles was confirmed by examining the cathodes after 12 MEC cycles using scanning electron microscopy and linear sweep voltammetry. Analysis of the anodic communities in these reactors revealed dominant populations of Geobacter sulfurreduces and Pelobacter propionicus. These results demonstrate that nickel powder can be used as a viable alternative to Pt in MECs, allowing large scale production of cathodes with similar performance to systems that use precious metal catalysts.  相似文献   

4.
Microbial electrolysis cells (MECs) provide a high-yield method for producing hydrogen from renewable biomass. One challenge for commercialization of the technology is a low-cost and highly efficient cathode. Stainless steel (SS) is very inexpensive, and cathodes made of this material with high specific surface areas can achieve performance similar to carbon cathodes containing a platinum catalyst in MECs. SS mesh cathodes were examined here as a method to provide a higher surface area material than flat plate electrodes. Cyclic voltammetry tests showed that the electrochemically active surface area of certain sized mesh could be three times larger than a flat sheet. The relative performance of SS mesh in linear sweep voltammetry at low bubble coverages (low current densities) was also consistent with performance on this basis in MEC tests. The best SS mesh size (#60) in MEC tests had a relatively thick wire size (0.02 cm), a medium pore size (0.02 cm), and a specific surface area of 66 m2/m3. An applied voltage of 0.9 V produced a high hydrogen recovery (98 ± 4%) and overall energy efficiency (74 ± 4%), with a hydrogen production rate of 2.1 ± 0.3 m3H2/m3d (current density of 8.08 A/m2, volumetric current density of 188 ± 19 A/m3). These studies show that SS in mesh format shows great promise for the development of lower cost MEC systems for hydrogen production.  相似文献   

5.
Microbial electrolysis cells (MECs) are often examined for hydrogen production using non-sustainable phosphate buffered solutions (PBS), although carbonate buffers have been shown to work in other bioelectrochemical systems with a platinum (Pt) catalyst. Stainless steel (SS) has been shown to be an effective catalyst for hydrogen evolution in MECs, but it has not been tested with carbonate buffers. We evaluated the combined using of SS cathodes and a bicarbonate buffer (BBS) at the applied voltages of 0.5, 0.7 and 0.9 V using a new inexpensive method for measuring gas production called the gas bag method (GBM). This method achieved an average error of only 5.0% based on adding known volumes of gas to the bag. Using the GBM, hydrogen production with SS and a BBS was 26.6 ± 1.8 mL which compared well to 26.4 ± 2.8 mL using Pt and BBS, and 26.8 ± 2.5 mL with a Pt cathode and PBS. Electrical energy efficiency was highest with a SS cathode and BBS at 159 ± 17%, compared to 126 ± 14% for the Pt cathode and BBS, and 134 ± 17% for a Pt cathode and PBS. The main disadvantage of the SS was a lower gas production rate of 1.1 ± 0.3 m3 H2-m−3 d−1 with BBS and 1.2 ± 0.3 m3 H2-m−3 d−1 with PBS, compared to 1.7 ± 0.4 m3 H2-m−3 d−1 with Pt and PBS. These results show that the GBM is an effective new method for measuring gas production of anaerobic gas production processes, and that SS and bicarbonate buffers can be used to effectively produce hydrogen in MECs.  相似文献   

6.
Platinum has excellent catalytic capabilities and is commonly used as cathode catalyst in microbial electrolysis cells (MECs). Its high cost, however, limits the practical applications of MECs. In this study, precious-metal-free cathodes were developed by electrodepositing NiMo and NiW on a carbon-fiber-weaved cloth material and evaluated in electrochemical cells and tubular MECs with cloth electrode assemblies (CEA). While similar performances were observed in electrochemical cells, NiMo cathode exhibited better performances than NiW cathode in MECs. At an applied voltage of 0.6 V, the MECs with NiMo cathode accomplished a hydrogen production rate of 2.0 m3/day/m3 at current density of 270 A/m3 (12 A/m2), which was 33% higher than that of the NiW MECs and slightly lower than that of the MECs with Pt catalyst (2.3 m3/day/m3). At an applied voltage of 0.4 V, the energy efficiencies based on the electrical energy input reached 240% for the NiMo MECs. These results demonstrated the great potential of using carbon cloth with Ni-alloy catalysts as a cathode material for MECs. The enhanced MEC performances also demonstrate the scale-up potential of the CEA structure, which can significantly reduce the electrode spacing and lower the internal resistance of MECs, thus increasing the hydrogen production rate.  相似文献   

7.
H2 can be produced from organic matter with a microbial electrolysis cell (MEC). To decrease the energy input and increase the H2 production rate of an MEC, a catalyst is used at the cathode. Platinum is an effective catalyst, but its high costs stimulate searching for alternatives, such as non-noble metal alloys. This study demonstrates that copper sheet coated with nickel-molybdenum, nickel-iron-molybdenum or cobalt-molybdenum alloys have a higher catalytic activity for the hydrogen evolution reaction than nickel cathodes, measured near neutral pH. However, the catalytic activity cannot be fully exploited near neutral pH because of mass transport limitation. The catalytic activity is best exploited at alkaline pH where mass transport is not limiting. This was demonstrated in an MEC with a cobalt-molybdenum coated cathode and anion exchange membrane, which produced 50 m3 H2 m−3 MEC d−1 (at standard temperature and pressure) at an electricity input of 2.5 kWh m−3 H2.  相似文献   

8.
Nickel foam (NF), stainless steel wool (SSW), platinum coated stainless steel mesh (Pt), and molybdenum disulfide coated stainless steel mesh (MoS2) electrodes have been proposed as catalysts for hydrogen gas production, but previous tests have primarily examined their performance in well buffered solutions. These materials were compared using two-chamber microbial electrolysis cells (MECs), and linear sweep voltammetry (LSV) in unbuffered saline solutions at two different initial pHs (7 and 12). There was generally no appreciable effect of initial pH on production rates or total gas production. NF produced hydrogen gas at a rate of 1.1 m3 H2/m3·d, which was only slightly less than that using Pt (1.4 m3 H2/m3·d), but larger than that obtained with SSW (0.52 m3 H2/m3·d) or MoS2 (0.67 m3 H2/m3·d). Overall hydrogen gas recoveries with SSW (29.7 ± 0.5 mL), MoS2 (28.6 ± 1.3 mL) and NF (32.4 ± 2 mL) were only slightly less than that of Pt (37.9 ± 0.5 mL). Total energy recoveries, based on the gas produced versus electrical energy input, ranged from 0.75 ± 0.02 for Pt, to 0.55 ± 0.02 for SSW. An LSV analysis showed no effect of pH for NF and Pt, but overpotentials were reduced for MoS2 and SSW by using an initial lower pH. At cathode potentials more negative than −0.85 V (vs Ag/AgCl), NF had lower overpotentials than the MoS2. These results provide the first assessment of these materials under practical conditions of high pH in unbuffered saline catholytes, and position NF as the most promising inexpensive alternative to Pt.  相似文献   

9.
Most microbial electrolysis cells (MECs) contain only a single set of electrodes. In order to examine the scalability of a multiple-electrode design, we constructed a 2.5 L MEC containing 8 separate electrode pairs made of graphite fiber brush anodes pre-acclimated for current generation using acetate, and 304 stainless steel mesh cathodes (64 m2/m3). Under continuous flow conditions and a one day hydraulic retention time, the maximum current was 181 mA (1.18 A/m2, cathode surface area; 74 A/m3) within three days of operation. The maximum hydrogen production (day 3) was 0.53 L/L-d, reaching an energy efficiency relative to electrical energy input of ηE = 144%. Current production remained relatively steady (days 3–18), but the gas composition dramatically shifted over time. By day 16, there was little H2 gas recovered and methane production increased from 0.049 L/L-d (day 3) to 0.118 L/L-d. When considering the energy value of both hydrogen and methane, efficiency relative to electrical input remained above 100% until near the end of the experiment (day 17) when only methane gas was being produced. Our results show that MECs can be scaled up primarily based on cathode surface area, but that hydrogen can be completely consumed in a continuous flow system unless methanogens can be completely eliminated from the system.  相似文献   

10.
Non-platinum based cathodes were recently developed by electrodepositing NiMo on carbon cloth, which demonstrated good electrocatalytic activity for hydrogen evolution in microbial electrolysis cells (MECs). To further optimize the electrodeposition condition, the effects of electrolyte bath composition, applied current density, and duration of electrodeposition were systematically investigated in this study. The developed NiMo catalysts were characterized with scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) and evaluated using chronopotentiometry and in MECs. The optimal condition for electrodeposition of NiMo on carbon cloth was determined as: a Mo/Ni mass ratio of 0.65 in electrolyte bath, an applied current density of 50 mA/cm2 and electrodeposition duration of 10 min. Under this condition, the NiMo catalyst has a formula of Ni6MoO3 with a nodular morphology. The NiMo loading on the carbon cloth was reduced to 1.7 mg/cm2 and the performance of MEC with the developed NiMo cathode was comparable to that with Pt cathode with a similar loading. This result indicates that a much lower cathode fabrication cost can be achieved compared to that using Pt catalyst, and thereby significantly enhancing the economic feasibility of the MEC technology.  相似文献   

11.
Molasses is by-product from sugar beet process and commonly used as raw material for ethanol production. However, the molasses wastewater possesses high level of chemical oxygen demand (COD), which needs to be properly treated before discharge. In this work, MEC technology, a promising method for hydrogen production from organic waste, was utilized to produce H2 from molasses wastewater. In this study, the feasibility of operating the MEC at low temperatures was evaluated since the average wastewater temperature in Harbin city is lower than 10 °C. In addition, the feasibility of using biocathode as an alternative to expensive platinum (Pt) as the cathode material was also examined. Both Pt catalyzed MECs and biocathodic MECs were operated at a low temperature of 9 °C. The overall hydrogen recovery of 72.2% (Eap = 0.6 V) was obtained when the Pt catalyst was used. In contrast, when a cheaper catalyst (biocathode; Eap = 0.6 V) was used, hydrogen can still be produced but at a lower overall hydrogen recovery of 45.4%. This study demonstrated that hydrogen could be generation from molasses wastewater at a low temperature using a cheaper cathode material (i.e., biocathode).  相似文献   

12.
Layered molybdenum disulfide (MoS2)–graphene composite is synthesized by a modified l-cysteine-assisted solution-phase method. The structural characterization of the composites by energy dispersive X-ray analysis, X-ray powder diffraction, Fourier transform infrared spectroscopy, XPS, Raman, and transmission electron microscope indicates that layered MoS2–graphene coalescing into three-dimensional sphere-like architecture. The electrochemical performances of the composites are evaluated by cyclic voltammogram, galvanostatic charge–discharge and electrochemical impedance spectroscopy. Electrochemical measurements reveal that the maximum specific capacitance of the MoS2–graphene electrodes reaches up to 243 F g−1 at a discharge current density 1 A g−1. The energy density is 73.5 Wh kg−1 at a power density of 19.8 kW kg−1. The MoS2–graphene composites electrode shows good long-term cyclic stability (only 7.7% decrease in specific capacitance after 1000 cycles at a current density of 1 A g−1). The enhancement in specific capacitance and cycling stability is believed to be due to the 3D MoS2–graphene interconnected conductive network which promotes not only efficient charge transport and facilitates the electrolyte diffusion, but also prevents effectively the volume expansion/contraction and aggregation of electroactive materials during charge–discharge process. Taken together, this work indicates MoS2–graphene composites are promising electrode material for high-performance supercapacitors.  相似文献   

13.
SmBaCoCuO5+δxCe0.9Gd0.1O1.95 (SBCCO–xGDC, x = 10, 30, 50, 60, wt%) composite cathodes have been investigated for their potential utilization in intermediate temperature solid oxide fuel cells (IT-SOFCs). The thermal expansion behavior shows that the thermal expansion coefficient (TEC) values of SBCCO cathode decrease with GDC addition. The TEC of SBCCO–50GDC cathode is 13.1 × 10−6 K−1 from 30 to 850 °C in air. By means of DC polarization and AC impedance spectroscopy, the electrochemical performance of SBCCO–xGDC composite cathodes on GDC electrolyte is examined. Results indicate that the proper addition of GDC could improve the performance of SBCCO cathode. The optimum content of GDC in the composite cathodes is 50 wt% with the polarization resistance (Rp) of 0.040 Ω cm2 at 800 °C. An electrolyte-supported single-cell configuration of SBCCO–50GDC/GDC/Ni–GDC attains a maximum power density of 628 mW cm−2 at 800 °C. Preliminary results indicate that SBCCO–50GDC is especially promising as a cathode for IT-SOFCs.  相似文献   

14.
Several alternative cathode catalysts have been proposed for microbial fuel cells (MFCs), but effects of salinity (sodium chloride) on catalyst performance, separate from those of conductivity on internal resistance, have not been previously examined. Three different types of cathode materials were tested here with increasingly saline solutions using single-chamber, air-cathode MFCs. The best MFC performance was obtained using a Co catalyst (cobalt tetramethoxyphenyl porphyrin; CoTMPP), with power increasing by 24 ± 1% to 1062 ± 9 mW/m2 (normalized to the projected cathode surface area) when 250 mM NaCl (final conductivity of 31.3 mS/cm) was added (initial conductivity of 7.5 mS/cm). This power density was 25 ± 1% higher than that achieved with Pt on carbon cloth, and 27 ± 1% more than that produced using an activated carbon/nickel mesh (AC) cathode in the highest salinity solution. Linear sweep voltammetry (LSV) was used to separate changes in performance due to solution conductivity from those produced by reductions in ohmic resistance with the higher conductivity solutions. The potential of the cathode with CoTMPP increased by 17–20 mV in LSVs when the NaCl addition was increased from 0 to 250 mM independent of solution conductivity changes. Increases in current were observed with salinity increases in LSVs for AC, but not for Pt cathodes. Cathodes with CoTMPP had increased catalytic activity at higher salt concentrations in cyclic voltammograms compared to Pt and AC. These results suggest that special consideration should be given to the type of catalyst used with more saline wastewaters. While Pt oxygen reduction activity is reduced, CoTMPP cathode performance will be improved at higher salt concentrations expected for wastewaters containing seawater.  相似文献   

15.
The development of efficient and economical cathode, operating at ambient temperature and neutral pH is a crucial challenge for microbial electrolysis cell (MEC) to become commercialize hydrogen production technology. In the present work, eight different electrodes are prepared by the electroplating of Ni, Ni–Co and Ni–Co–P on two base metals i.e., Stainless Steel 316 and Copper separately to use as cathode in MEC. Electrodeposited cathode materials have been characterized by XRD, XPS, FESEM, EDX and linear voltammetry. The fabricated cathodes show higher corrosion stability with improved electro-catalytic performance for the hydrogen production in the MECs as compared to the bare cathodes (SS316 and Cu). Data obtained from linear voltammetry and MEC experiments show that developed cathode possess four times higher intrinsic catalytic activity in comparison to bare cathode. Electrodeposited cathodes are intensively examined in membrane-less MEC, operating under applied voltage of 0.6 V in batch mode at 30 ± 2 °C temperature, in neutral pH with acetate as substrate and activated sludge as inoculum. Ni–Co–P electrodeposit on Stainless Steel 316 cathode gives maximum hydrogen production rate of 4.2 ± 0.5 m3(H2)m−3d−1, columbic efficiencies 96.9 ± 2%, overall hydrogen recovery 90.3 ± 4%, overall energy efficiency 241.2 ± 5%, volumetric current density 310 ± 5 Am−3. The net energy recovery and COD removal are 4.25 kJ/gCOD and 61%, respectively. Prepared cathodes show stable performance for continuous 5 batch cycle operations in MEC.  相似文献   

16.
This study aims at investigating the effects of platinum (Pt) loadings on the cathodic reactions in Single Chamber Microbial Fuel Cells (SCMFCs) and developing cost-effective MFC operational protocols. The power generation of SCMFCs was examined with different Pt loadings (0.005–1 mgPt/cm2) on cathodes. The results showed that the power generation of the SCMFCs with 0.5–1 mgPt/cm2 were the highest in the tests, decreased 10–15% at 0.01–0.25 mgPt/cm2, and decreased further 10–15% at 0.005 mgPt/cm2. The SCMFCs with Pt-free cathode (graphite) had the lowest power generation. In addition, the power generation of SCMFCs with different Pt loadings were compared in raw wastewater (Chemical oxygen demand (COD): 0.36 g/L) and wastewater enriched with sodium acetate (COD: 2.95 g/L). The solution conductivity in SCMFCs decreased with the degradation of organic substrates. Daily polarization curves (VI) showed a decrease in current generation and an increase in ohmic losses over the operational period (8 days). The SCMFCs (with 0.5–1 mgPt/cm2 at cathode) fed with wastewater and sodium acetate (NaOAc) reached the highest power generation (786 mW/m2), while the SCMFCs (with 0.5–1 mgPt/cm2 at cathode) fed only with wastewater obtained the lower power generation (81 mW/m2). The study demonstrated that lowering the Pt loadings in two magnitude orders (1 to 0.01, 0.5 to 0.005 mgPt/cm2) only reduced the power generation of 15–30%, and this reduction of the power generation become less substantial with the decrease in the solution conductivity of SCMFCs.  相似文献   

17.
A highly active and stable bimetallic nano-hybrid catalyst Graphene–Cobalt–Platinum (G–Co–Pt) is proposed for the enhanced and cost effective generation of hydrogen from Sodium Borohydride. Three different nano-hybrid catalysts namely Graphene–Cobalt (G–Co), Graphene–Platinum (G–Pt) and Graphene–Cobalt–Platinum (G–Co–Pt) are synthesized, characterized using XRD, FTIR, SEM, HRTEM, EDAX and Cyclic voltammetry (CV) analysis and tested for hydrogen generation. The activity and stability of the catalysts are analyzed by estimating the turnover frequency (TOF), the electrochemically active surface area (ECSA), the percentage decay of current density over ten cycles of CV and the decay in the rate of hydrogen generation with the age of catalyst. Among the three catalysts G–Co–Pt exhibits the highest catalytic activity (TOF = 107 min−1, ECSA = 75.32 m2/gm) and stability. The evaluated value of activation energy of the catalytic hydrolysis using G–Co–Pt is 16 ± 2 kJ mol−1.  相似文献   

18.
Electricity production from carbon monoxide (CO) in a microbial fuel cell (MFC) has recently been demonstrated. Efficient operation of this MFC requires a CO-tolerant and preferably inexpensive cathode. Pyrolised CoTMPP, FeTMPP, and Co/FeTMPP gas diffusion cathodes were tested in MFCs operated on acetate or CO. When the MFC was fed with acetate the best cathode performance was obtained when using a Co/FeTMPP (3:1) cathode with a Me catalyst load of 0.5 mg cm−2, although this performance was slightly lower than that obtained with a cathode containing 0.5 mg-Pt cm−2. Tests using a MFC operated on CO showed a higher power output when using the Co/FeTMPP cathode when compared both with CoTMPP and Pt cathodes.  相似文献   

19.
The stability of La0.6Sr0.4Co0.2Fe0.8O3−δ impregnated Y2O3 stabilized ZrO2 (LSCF–YSZ) cathodes was investigated under the condition of open circuit or current polarization at 750 °C in air. The electrochemical measurement and the microstructure characteristic show that the flattening of LSCF particles has great contribution to the increase of resistance of LSCF–YSZ cathodes after 500 h heat treatment at 750 °C. Microstructure coarsening and the damage of well-connected porous structure are main reasons of the performance degradation for LSCF–YSZ cathodes testing at 200 mA cm−2 and 750 °C in air. Higher current density of 500 mA cm−2 applying on cathodes accelerates degradation processes. X-ray photoelectron spectroscopy (XPS) shows that Sr concentration on the cathode surface decreases after current polarization, which plays a main role in performance activation processes observed at the beginning stage. The enhancement of cobalt activity in LSCF lattice by current polarization increases the conductivity and decreases the stability of LSCF–YSZ cathodes.  相似文献   

20.
In this paper, a systematic investigation was carried out of activities at 80 °C of Pt supported on Sibunit-1562 graphitized carbon in the electroreduction of oxygen in the polymer electrolyte fuel cell. Pt content in the Pt/Sibunit-1562 catalysts was 20, 40, and 60 wt.% and Pt load at the cathode was varied in the 200–6.25 μgPt cm−2 interval. The results were compared with the activity of commercial 20 wt.% Pt/Vulcan XC-72 catalyst. To optimize the transport properties of the cathode layer and maintain its thickness upon using Pt/Sibunit −1562 catalysts with varied Pt content and Pt loads a definite amount of Vulcan-XC-72 carbon support was added to the cathode catalytic inks. Higher activity of Pt/Sibunit-1562 catalysts was found as compared to that of commercial 20 wt.% Pt/Vulcan XC-72 with similar particle size of the active component.  相似文献   

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