Feasibility of preparing additive manufactured porous stainless steel felts with mathematical micro pore structure as novel catalyst support for hydrogen production via methanol steam reforming

In this paper, an additive manufacturing prepared porous stainless steel felt (AM-PSSF) is proposed as a novel catalyst support for hydrogen production via methanol steam reforming (MSR). In the method, 316 L stainless steel powder with diameter of 15–63 μm is processed by the additive manufacturing technology of selective laser melting (SLM). To accomplish the preparation, the reforming chamber where the AM-PSSF is embedded is firstly divided into an all-hexahedron mesh. Then, the triply periodic minimal surface (TPMS) unit with mathematical form, high interconnectivity and large specific surface area is mapped into the hexahedrons based on shape function, forming the fully connected three-dimensional (3D) micro pore structure of the AM-PSSF. By correlating the mathematical parameter and the porosity of the TPMS unit, and taking into account the SLM process, the porosity of the AM-PSSF is well controlled. Based on the designed 3D pore structure model, the AM-PSSF is produced using standard SLM process. The application of the AM-PSSF as catalyst support for hydrogen production through MSR indicates that: 1) both the naked and catalyst-coated AM-PSSF have the characteristics of high porosity, large specific surface area and high connectivity; 2) the MSR hydrogen production performance of the AM-PSSF is better than that of the commercial stainless steel fiber sintered felt. The feasibility of AM-PSSF as catalyst support for MSR hydrogen production may pave a better way to balance different requirements for catalyst support, thanks to the excellent controllability provided by AM on both the external shape and the internal pore structure, and to the produced rough surface morphology that benefits the catalyst adhesion strength. In addition, catalyst support with pore structures that are more accommodated with the flow field and the reaction rate of MSR reaction may be prepared in future, since the entire catalyst support structure, from macro scale to micro scale, is under control.     

PtIr alloy nanowire assembly on carbon cloth as advanced anode catalysts for methanol oxidation

The interconnecred PtIr alloy nanowires were uniformly deposited on carbon cloth via One-step wet chemistry method, which diameter is averaged to be 5 nm with a length of 50–200 nm. The carbon cloth supported PtIr nanowire assembly (PtIr NA/CC) shows a larger electrochemical active surface area (ECSA) due to its 3D nanostructure and a high CO-resistance as a result from the synergistic effect of PtIr alloy. The PtIr NA/CC exhibits an extremely high mass activity and a reliable long-term stability toward methanol oxidation reaction (MOR). The superior catalytic performance on MOR can match and even surpass those best Pt-based nanowires reported recently in the literature.     

Methanol electrooxidation at nickel-modified rhodanine self assembled monolayer films: A new class of multilayer electrocatalyst

Nickel modified rhodanine (Rh) self-assembled monolayer films (Rh-SAM/Ni) were fabricated on copper from 10.0 mM Rh containing methanol. The films were characterized with the help of scanning electron microscopy (SEM), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDX) techniques. The methanol oxidation activity of the Rh-SAM/Ni electrode was tested in 1.0 M methanol containing 0.1 M KOH solution using many electrochemical techniques. The results indicated that well-ordered and very homogeneously distributed Rh-SAM films were assembled over the copper surface. The rate of methanol electrooxidation reaction can be enhanced by modifying copper surface with Rh-SAM/Ni multi-layer film. The enhanced activity was related to increasing active sites over the surface for adsorption and oxidation of methanol as well as facilitating oxidation or desorption of adsorpted intermediates of the process. It was suggested that the Rh-SAM layer could be a candidate supporting material for fabricating direct methanol fuel cell (DMFCs) anodes.     

Synthesis of carbon nanofibers/poly(para-phenylenediamine)/nickel particles nanocomposite for enhanced methanol electrooxidation

Several studies have been conducted on direct methanol fuel cells (DMFCs) to resolve major issues such as the high cost of the catalyst and the poisoning of the electrode. Herein, a low-cost catalyst based on nickel particles (NiPs), carbon nanofibers (CNF) and poly(para-phenylenediamine) (PpPD) was carried out using a simple electrochemical method. The morphology and structure of the nanocomposite electrodes are characterized by field-emission gun scanning electron microscopy coupled with an energy dispersive X-ray detector, X-ray diffraction, Fourier transform infrared spectroscopy and Raman spectroscopy. The effects of various parameters such as the PpPD film thickness and the NiPs content on the electrocatalytic performance of CPE/CNF/PpPD/NiPs are evaluated which lead to the optimized composition. The results of the methanol electrooxidation reaction at room temperature showed that the optimized CPE/CNF/PpPD/NiPs nanocomposite exhibits a high catalytic activity (I_p = 38.11 mA cm⁻²), good stability and durability for more than 6 h in comparison with CPE/CNF/NiPs. These findings truly highlight the synergetic effect of CNF/PpPD in enhancing the electrochemical activity and stability and the vast potential of CPE/CNF/PpPD/NiPs as low-cost catalyst and electrodes for DMFCs.     

A comparison of two hydrogen storages in a fossil-free direct reduced iron process

Hydrogen direct reduction has been proposed as a means to decarbonize primary steelmaking. Preferably, the hydrogen necessary for this process is produced via water electrolysis. A downside to electrolysis is the large electricity demand. The electricity cost of water electrolysis may be reduced by using a hydrogen storage to exploit variations in electricity price, i.e., producing more hydrogen when the electricity price is low and vice versa. In this paper we compare two kinds of hydrogen storages in the context of a hydrogen direct reduction process via simulations based on historic Swedish electricity prices: the storage of gaseous hydrogen in an underground lined rock cavern and the storage of hydrogen chemically bound in methanol. We find the methanol-based storages to be economically advantageous to lined rock caverns in several scenarios. The main advantages of methanol-based storage are the low investment cost of storage capacity and the possibility to decouple storage capacity from rate capacity. Nevertheless, no storage option is found to be profitable for historic Swedish electricity prices. For the storages to be profitable, electricity prices must be volatile with relatively frequent high peaks, which has happened rarely in Sweden in recent years. However, such scenarios may become more common with the expected increase of intermittent renewable power in the Swedish electricity system.     

Recent advances in two-dimensional Pt based electrocatalysts for methanol oxidation reaction

Direct methanol fuel cells (DMFCs) had been attracted considerable attention for its advantages of high energy density, simplified systems and readily transportation and storage of methanol. However, the notoriously sluggish kinetics of methanol oxidation reaction (MOR) of the anode reaction, had greatly affected the commercialization of DMFCs. On one hand, Pt based catalyst are still the most effective MOR catalysts, while the high cost caused by the high loadings of electrocatalyst to compensate the low MOR activity impedes the wide accessible of DMFCs. In addition, the occurrence of catalyst poisoning owing to the strong interaction between Pt and carbon monoxide (CO) generated during the MOR processing, further leading to the fast decay in the performance and stability of MOR electrocatalysts. Two-dimensional (2D) Pt based nanostructures is regarded to be one promising and effective class of MOR electrocatalysts, and attracted much attention due to the high electron mobility, highly exposed active sites, and extraordinary thermal conduction. In this review, the mechanism of MOR was firstly introduced, and then the synthesis conditions, structure characteristics and methanol oxidation performances both in acidic and alkaline dielectric of 2D Pt based nanocatalysts were introduced. Subsequently, we briefly analyzed the structural characteristics of 2D Pt based nanocatalysts and their advantages, including the low platinum loadings, high specific surface area and majority of atomic active sites exposed. Finally, the opportunities and challenges for designing of advanced 2D Pt based nanocatalysts was proposed and discussed.     

A remarkable three-component RuO2-MnCo2O4/rGO nanocatalyst towards methanol electrooxidation

A three-part nano-catalyst including ruthenium oxide, manganese cobalt oxide, and reduced graphene oxide nanosheet in form of RuO₂-MnCo₂O₄/rGO is synthesized by one-step hydrothermal synthesis. The material is placed on a glassy carbon electrode (GCE) for electrochemical studies. The ability of these nano-catalysts in the oxidation process of methanol in an alkaline medium for usage in direct methanol fuel cells (DMFC) was examined with electrochemical tests of cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The effect of the addition of rGO to the nanocatalyst structure in the methanol oxidation reaction (MOR) process was investigated. We introduced the RuO₂-MnCo₂O₄/rGO as a nanocatalyst with excellent cyclic stability of 97% after 5000 cycles in the MOR process. Besides, the study of the Tafel plots and the effect of temperature and scan rate in the MOR process showed that RuO₂-MnCo₂O₄/rGO nanocatalyst has better electrochemical properties than MnCo₂O₄ and RuO₂-MnCo₂O₄. This high electrocatalytic activity could be related to the synergistic effect of placement of metal oxides of ruthenium, manganese, and cobalt near each other and putting them on rGO, which enhances conductivity and surface area and improve electron transfer. The decrease in the resistance against charge transfer and the increment in the anodic current density illustrated that the reaction rate is enhanced at higher temperature. Thus RuO₂-MnCo₂O₄/rGO shows robust stability and superior performance for MOR.     

A hybrid fuel cell system integrated with methanol steam reformer and methanation reactor

In this paper, a hybrid fuel cell system integrated with methanol steam reformer and methanation reactor is demonstrated. Methanol steam reformer employed in this system is to produce hydrogen-rich reformate in connection with a methanation reactor to reduce the carbon monoxide content effectively, and the reformate gas is sent into a low-temperature polymer electrolyte fuel cell for direct electric power generation. The optimum conditions (temperature, water to methanol ratio, and space velocity) for methanol steam reforming (MSR) reaction and methanation (MET) reaction are verified by experiments. A comparison between pure hydrogen, reformate surrogate, and actual reformate is performed. The results show that the power density of this hybrid system achieves 245.2 mW/cm² while it achieves 268.8 mW/cm² when employing pure hydrogen as the fuel. An alternative novel method to solve the problem of hydrogen storage and transportation is provided and the in-situ hydrogen production and utilizing through low-temperature fuel cell system is realized, which is helpful to accelerate the commercialization process of the fuel cell.     

Enhanced electrocatalytic performance of Pt nanoparticles immobilized on novel electrospun PVA@Ni/NiO/Cu complex bio-nanofiber/chitosan based on Calotropis procera plant for methanol electro-oxidation

Bioinspired Ni/NiO nanocomposite was synthesized in the Calotropis procera wood and its size and structure were confirmed by transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). The green and environmental friendly approach was performed for the preparation of copper nanocomplex (CC) under ultrasonic irradiation. Polyvinyl alcohol (PVA) nano-biofibers containing Ni/NiO nanocomposite and copper nanocomplex were obtained by electrospinning method. This novel bio nanocomposite was characterized by field-emission scanning electron microscope (FESEM), TEM, and atomic force microscopy (AFM) for further investigation. Novel Pt/PVA@Ni/NiO/Cu nanocomplex/chitosan (Pt/PVA@NOCC/CH) was synthesized and its catalytic performance was studied towards methanol electro-oxidation. Pt/PVA@NOCC/CH catalyst exhibits enhanced electrocatalytic performance towards methanol oxidation (MO), compared to Pt/PVA/CH and Pt/PVA@NOCC with respect to its better stability, larger electrochemically active surface area, enhanced mass activity, and improved resistance to poisoning. By and large, Pt/PVA@NOCC/CH is known as a promising electrocatalyst for fuel cells.     

Electrochemical preparation of Pt-based catalysts on carbon paper treated with Sn sensitization and Pd activation

CoRuPt and CoPtRu catalysts were prepared on carbon paper (CP) using various electrochemical processes including Sn sensitization, Pd activation, Co electrodeposition and galvanic displacement. The Sn-Pd process is a surface treatment that guarantees a larger number of nucleation sites on CP for subsequent Co electrodeposition by modifying the surface to be more hydrophilic. Co particles were deposited on Sn-Pd-treated CP (SCP) by controlling deposition potential and time. Then, Pt and Ru galvanic displacements were performed on the Co particles to form CoRuPt/SCP and CoPtRu/SCP catalysts. Electrochemical measurements confirmed that the CoRuPt/SCP - 1 catalyst with a 1.02 Pt/Ru surface molar ratio showed a peak potential of 741 mV (vs. NHE) for methanol oxidation and 637 mV for carbon monoxide stripping. These values were 80 and 8 mV lower, respectively, than those of a PtRu/C commercial catalyst.