Comparison of cathode catalyst binders for the hydrogen evolution reaction in microbial electrolysis cells

Nafion is commonly used as a catalyst binder in many types of electrochemical cells, but less expensive binders are needed for the cathodes in microbial electrolysis cells (MECs) which are operated in neutral pH buffers, and reverse electrodialysis stacks (RED),which use thermolytic solutions such as ammonium bicarbonate. Six different binders were examined based on differences in ion exchange properties (anionic: Nafion, BPSH20, BPSH40, S-Radel; cationic: Q-Radel; and neutral: Radel, BAEH) and hydrophobicity based on water uptake (0%, Radel; 17–56% for the other binders). BPSH40 had similar performance to Nafion based on steady-state polarization single electrode experiments in a neutral pH phosphate buffer, and slightly better performance in ammonium bicarbonate. Three different Mo-based catalysts were examined as alternatives to Pt, with MoB showing the best performance under steady-state polarization. In MECs, MoB/BPSH40 performed similarly to Pt with Nafion or Radel binders. The main distinguishing feature of the BPSH40 was that it is very hydrophilic, and thus it had a greater water content (56%) than the other binders (0–44%). These results suggest the binders for hydrogen evolution in MECs should be designed to have a high water content without sacrificing ionic or electronic conductivity in the electrode.     

Optimization of NiMo catalyst for hydrogen production in microbial electrolysis cells

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.     

Process kinetics for the electrocatalytic hydrogen evolution reaction on carbon-based Ni/NiO nanocomposite in a single-chamber microbial electrolysis cell

To explore the process kinetics of hydrogen evolution reaction (HER) on carbon-based Ni/NiO nanocomposite in the microbial electrolysis cells (MECs), the performance was systematically studied by different time-course sampling of five parallel single-chamber MECs operated under identical operating conditions, which included the electrochemical performance of anodes and cathodes, and the mechanism and kinetics of HER. It was hypothesized that the decreased performance of the nickel cathodes was due to corrosion and Ni dissolution. These results provide valuable insights into the effects of long-term operation on MEC performance.     

Defects and doping engineered two-dimensional o-B2N2 for hydrogen evolution reaction catalyst: Insights from DFT simulation

In this work, a detailed investigation of the structural and electronic properties and hydrogen evolution reaction (HER) activity of the pristine, vacancy and carbon (C) doped o-B₂N₂ monolayer is carried out using first-principles based density functional theory. The creation of vacancy and C doping modulates structural and electronic properties of the monolayers and enhances the HER activity of o-B₂N₂. The BN vacancy defect, C doping at B and N sites in the monolayer enhances the magnitude of HER activity by 77.34%, 86.71% and 83.59% as compared to pristine monolayer. The modulation in the HER activity of the o-B₂N₂ is due to the redistribution of charge after induction of vacancy and dopant. Our results suggest that the C doping makes o-B₂N₂ metallic which can be utilized as an “electrocatalyst” whereas BN vacancy defected o-B₂N₂ monolayer is semiconducting with a band gap of ～1 eV and can be used as “photocatalyst” for HER activity.     

Heterostructured Co3O4/VO2 nanosheet array catalysts on carbon cloth for hydrogen evolution reaction

Developing highly efficient, low-cost, and robust water splitting hydrogen production catalysts is critical for hydrogen energy applications. This study presents the synthesis of Co₃O₄/VO₂ heterogeneous nanosheet structures on carbon cloth (Co₃O₄/VO₂/CC). The obtained Co₃O₄/VO₂/CC hybrid catalyst has a low overpotential of 108 mV at a current density of 10 mA cm^?2, a Tafel slope of 98 mV dec^?1, and high stability in 1.0 M KOH for 10 h. The experimental results and density functional theory (DFT) calculations results also show that Co₃O₄ coupled with VO₂ in Co₃O₄/VO₂/CC can optimize hydrogen adsorption energy and facilitate electron transport, thereby accelerating the catalytic kinetics for hydrogen evolution reaction (HER). This work also provided an alternative method to design and construct non-noble metal oxide-based catalysts for alkaline hydrogen production.     

Nickel powder blended activated carbon cathodes for hydrogen production in microbial electrolysis cells

Although pure Ni catalysts can achieve a hydrogen production rate similar to Pt in microbial electrolysis cells (MECs), a reduction in the amount of Ni used is needed to reduce the cost. In this study, nickel powder (pNi) was blended with activated carbon (AC) to reduce the mass of Ni used, while improving catalytic activity for the hydrogen evolution reaction (HER) by increasing the active surface area. Ni powder blended AC cathodes (AC-pNi) were fabricated at different nickel powder loadings (4.8, 19, 46 mg/cm² with AC and 77 mg/cm² without AC as control). AC-pNi4.8 (Ni loading: 4.8 mg/cm²) produced higher hydrogen production rates (0.38 ± 0.04 L-H₂/L-d) than pNi77 (0.28 ± 0.02 L-H₂/L-d) with a 16 times less Ni loading. Cathodic hydrogen recovery of using the AC-pNi4.8 (98 ± 5%) was also higher than pNi77 (82 ± 4%), indicating catalytic activities were improved by AC blending. Nickel dissolution into the catholyte after completion of each cycle was negligible for AC-pNi4.8 (<0.2 mg/L), while Ni dissolution was detected for pNi77 (5–10 mg/L). These results indicate that AC blending with Ni powder can improve hydrogen production in MECs while minimizing the amount of Ni in the cathode.     

Electrolyte effects on hydrogen evolution and solution resistance in microbial electrolysis cells

Protonated weak acids commonly used in microbial electrolysis cell (MEC) solutions can affect the hydrogen evolution reaction (HER) through weak acid catalysis, and by lowering solution resistance between the anode and the cathode. Weak acid catalysis of the HER with protonated phosphate, acetate, and carbonate electrolyte species improved MEC performance by lowering the cathode's overpotential by up to 0.30 V at pH 5, compared to sodium chloride electrolytes. Deprotonation of weak acids into charged species at higher pHs improved MEC performance primarily by increasing the electrolyte's conductivity and therefore decreasing the solution resistance between electrodes. The potential contributions from weak acid catalysis and solution resistance were compared to determine whether a reactor would operate more efficiently at lower pH because of the HER, or at higher pH because of solution resistance. Phosphate and acetate electrolytes allowed the MEC to operate more efficiently under more acidic conditions (pH 5). Carbonate electrolytes increased performance from pH 5 to 9 due to a relatively large increases in conductivity. These results demonstrate that specific buffers can substantially contribute to MEC performance through both reduction in cathode overpotential and solution resistance.     

Recent advances in cobalt disulfide for electrochemical hydrogen evolution reaction

Hydrogen production by water electrolysis is the most promising green hydrogen supply method in the future. Electrocatalytic hydrogen evolution reaction (HER), an essential step in water electrolysis, has received continuous interest for a long time. Noble metal-based electrocatalysts exhibit excellent performance for HER, while their high price, limited reserves, and insufficient durability limit their large-scale applications. Transition metal sulfides (TMSs) have been extensively studied as potential alternative catalysts, among which cobalt disulfide (CoS₂) stands out due to its unique structure, low price, and good electrical conductivity. Although remarkable progress has been made, the catalytic activity and stability of CoS₂ electrode materials themselves are still insufficient for large-scale industrial applications, so effective improvement of the HER catalytic performance of CoS₂ remains the focus of research. In this review, we briefly outline the reaction mechanism of HER, focusing on strategies to improve the catalytic performance of CoS₂, including morphology engineering, carbon materials combination, heteroatom doping, and heterostructure construction. Furthermore, the key challenges and opportunities for CoS₂ electrode materials as an electrocatalytic material for HER are discussed.     

Novel nanostructured electrocatalysts for hydrogen evolution reaction in neutral and weak acidic solutions

Microbial electrolysis cells (MECs) provide an innovative bioelectrochemical approach for hydrogen production using microorganisms as biocatalysts. The development of cost-effective cathodes for near-neutral pH and ambient temperature conditions is the most critical challenge for the practical application of MEC technology. In this study, the electrocatalytic properties of electrodeposited onto carbon felt NiFe-, NiFeP- and NiFeCoP-nanostructures towards HER in neutral and weak acidic solutions were investigated. The voltage needed to initiate hydrogen production and the current production rates were estimated from obtained linear voltammograms. The developed composite materials possess much higher catalytic activity than bare carbon felt. The highest current production rate corresponding to 1.7 ± 0.1 m³H₂/day/m² was achieved with NiFeCoP/carbon felt electrodes. In addition, the applied modifications result in improvement of the corrosion resistance. The obtained results demonstrate that Ni-based nanomodified materials are promising electrocatalysts for HER in near-neutral electrolytes and could be applied as cathodes in MECs.     

Mechanism of heteroatom-doped Cu5 catalysis for hydrogen evolution reaction

Developing high-performance hydrogen evolution reaction (HER) electrocatalysts is of great significance for solving the global energy crisis. Cluster has great application potential in the field of catalysis due to their unique quantum size effect and high specific surface area. Herein, the HER catalytic performance of Cu₅ cluster were regulated and optimized by doping heteroatoms. The Gibbs free energy calculation shows that the catalytic activity of Cu₅Ni and Cu₅Pt is comparable to that of Pt-based catalysts, and the Gibbs free energy value of Cu₅C can even reach 0.005 eV, indicating its much higher catalytic performance than that of other catalysts. Thus, the catalytic activity of Cu₅ clusters is optimized by doping non-metal and transition metal atoms to regulate the geometric and electronic structure of Cu₅. It was found that Cu₅Ni, Cu₅Pt and Cu₅C are potential catalysts to replace Pt-based catalysts for reducing the cost and achieving large-scale hydrogen production. This work provides a new avenue to regulate the catalytic performance of clusters, which is helpful for the further development and application of clusters in the field of catalysis.     

Improved hydrogen recovery in microbial electrolysis cells using intermittent energy input

Microbial electrolysis cell (MEC) is a bioelectrochemical technology that can produce hydrogen gas from various organic waste/wastewater. Extra voltage supply (>0.2 V) is required to overcome cathode overpotential for hydrogen evolution. In order to make MEC system more sustainable and practicable, it is necessary to minimize the external energy input or to develop other alternative energy sources. In this study, we aimed to improve the energy efficiency by intermittent energy supply to MECs (setting anode potential = −0.2 V). The overall gas production was increased up to ∼40% with intermittent energy input (on/off = 60/15sec) compared to control reactor. Cathodic hydrogen recovery was also increased from 62% for control MEC to 69–80% for intermittent voltage application. Energy efficiency was increased by 14–20% with intermittent energy input. These results show that intermittent voltage application is very effective not only for energy efficiency/recovery but also for hydrogen production as compared with continuous voltage application.     

Amorphous MoS2 nanosheets on MoO2 films/Mo foil as free-standing electrode for synergetic electrocatalytic hydrogen evolution reaction

A facile oxidation-sulfidation strategy is proposed to fabricate the vertically aligned amorphous MoS₂ nanosheets on MoO₂ films/Mo foil (MF) as free-standing electrode, which features as the integration of three merits (high conductivity, abundant exposures of active sites, and enhanced mass transfer) into one electrode for hydrogen evolution reaction (HER). Density functional theory (DFT) calculations reveal the strong interaction between MoS₂ and MoO₂, which can enhance the intrinsic conductivity with narrow bandgap, and decreases hydrogen adsorption free energy (ΔG_H1 = ~0.06 eV) to facilitate the HER process. Benefiting from the unique hierarchical structure with amorphous MoS₂ nanosheets on conductive MoO₂ films/MF to facilitate the electron/mass transfer by eliminate contact resistance, controllable number of stacking layers and size of MoS₂ slabs to expose more edge sites, the optimal MoS₂/MoO₂/MF exhibits outstanding activity with overpotential of 154 mV at the current density of 10 mA cm⁻², Tafel slope of 52.1 mV dec⁻¹, and robust stability. Furthermore, the intrinsic HER activity (vs. ECSA) on MoS₂/MoO₂/MF is significantly enhanced, which shows 4.5 and 18.6 times higher than those of MoS₂/MF and MoO₂/MF at overpotential of 200 mV, respectively.     

A new cathodic electrode deposit with palladium nanoparticles for cost-effective hydrogen production in a microbial electrolysis cell

Microbial electrolysis cell (MEC) provides a sustainable way for hydrogen production from organic matters, but it still suffers from the lack of efficient and cost-effective cathode catalyst. In this work carbon paper coated with Pd nanoparticles was prepared using electrochemical deposition method and used as the cathodic catalyst in an MEC to facilitate hydrogen production. The electrode coated with Pd nanoparticles showed a lower overpotential than the carbon paper cathode coated with Pt black. The coulombic efficiency, cathodic and hydrogen recoveries of the MEC with the Pd nanoparticles as catalyst were slightly higher than those with a Pt cathode, while the Pd loading was one order of magnitude less than Pt. Thus, the catalytic efficiency normalized by mass of the Pd nanoparticles was about fifty times higher than that of the Pt black catalyst. These results demonstrate that utilization of the cathode with Pd nanoparticles could greatly reduce the costs of the cathodic catalysts when maintaining the MEC system performance.     

Doping sp-hybridized B atoms in graphyne supported single cobalt atoms for hydrogen evolution electrocatalysis

Electrochemical water splitting to hydrogen is considered as a promising approach for clean H₂ production. However, developing highly active and inexpensive electrocatalysts is an important part of the hydrogen evolution reaction (HER). Herein, we present a multifaceted atom (sp²-and sp-hybridized boron) doping strategy to directly fine-modify the electronic structures of the active site and the HER performance by the density functional theory calculations. It is found that the binding strength between the Co atom and the B doped graphyne nanosheets can be enhanced by doping B atoms. Meanwhile, the Co@B₁-GY and Co@B₂-GY catalysts exhibit good thermodynamic stability and high HER catalytic activity. Interestingly, the Co@B₂-GY catalyst has an ideal HER performance with the ΔG_H* value of −0.004 eV. Moreover, the d-band center of the Co atoms is upshifted by the sp²-or sp-hybridized B dopants. The concentrations of the sp-hybridized B atoms have a positive effect on the electrons transformation of the Co atoms. The interaction between the H and Co atoms becomes strong with the increase of the concentrations of the sp-hybridized B atoms and thus the corresponding catalysts show sluggish HER kinetics. This investigation could provide useful guidance for the experimental groups to directly and continuously control the catalytic activity towards HER by precisely doping multifaceted atoms.     

Fe-Cu coated nickel mesh usage as cathode catalyst for hydrogen evolution reaction

Nickel mesh electrodes were used as the working electrode. Iron and copper were electrochemically deposited on the nickel mesh in different amounts. When electrochemical coatings had been carried out, different currents were passed from the circuit at different times and coatings were accumulated at constant load. The prepared electrodes called as FexCux, FexCu3x and FexCu9x and these electrodes have been used for hydrogen evolution reaction (HER). The surface morphologies were investigated by scanning electron microscopy. The HER activity is assessed by recording cathodic current–potential curves, cyclic voltammetry, electrochemical impedance spectroscopy. The results show that FexCu9x catalysts have a compact and porous structure as well as good electrocatalytic activity for the HER in alkaline media.     

Catalytic activity for hydrogen evolution reaction of Janus monolayer MoXTe (X=S,Se)

At present, the precious metal Pt is a common catalyst for large-scale hydrogen evolution reaction (HER) production of hydrogen, but due to its high price and scarcity, finding an innovative catalyst has become the key to electrocatalytic hydrogen evolution. Here, the HER electrocatalytic activity of Janus MoXTe (X = S, Se) monolayers was investigated through first-principles calculations. Mo vacancy, X vacancy and Te vacancy were introduced into 2H, 1T, and 1T’ phase respectively and their stability was studied. The results show that the introduction of vacancy can improve the electrocatalytic hydrogen evolution performance. Particularly, the Gibbs free energies (ΔG_H) of Te vacancy of 2H phase MoSTe and MoSeTe are close to zero (ΔG_H = 0.03, −0.05 eV, respectively), and has the highest exchange current density. We further find that the conductivity of 2H phase MoSTe and MoSeTe is enhanced after introducing Te vacancy. In details, H get 1.86 and 1.43 e on V_Te in 2H phase MoSTe and MoSeTe. The bond between S and H is more stable, H is better adsorbed on the catalyst, and the performance is improved. Our research provides a strategy for designing MoXTe monolayer electrocatalysts, which are predicted to be employed in HER catalysts with low cost and high performance.     

Repression of hydrogen uptake using conjugated oligoelectrolytes in microbial electrolysis cells

DSBN+, a conjugated oligoelectrolyte (COE), was added to microbial electrolysis cells (MECs) to improve hydrogen recovery. The volume of hydrogen gas recovered in a fed-batch cycle of mixed culture MECs increased by 126× compared to controls (no COE addition), mainly by preventing the loss of hydrogen to methane production. Performance in pure culture MECs fed with Geobacter sulfurreducens increased by factors of 10.5 in terms of energy yield, 2.1 in COD removal, and 11.8 in hydrogen yield. Hydrogen gas recycling was reduced, and the volume of hydrogen gas recovered increased by 6.5× compared to controls. Minimal methane production and a lack of hydrogen gas uptake by G. sulfurreducens suggested that the COEs increased hydrogen recoveries by interfering with hydrogen uptake by hydrogenotrophic methanogens but also by exoelectrogenic bacteria. COEs may therefore be useful for inhibiting the activities of certain hydrogenases, although the mechanism of inhibition needs further investigation.