Enhancement of hydrogen evolution reaction by Pt nanopillar-array electrode in alkaline media and the effect of nanopillar length on the electrode efficiency

Pt nanopillar-array 3D electrodes with nanopillar length of 150, 450 and 900 nm and nanopillar density of ~10⁹ cm⁻² were fabricated. Their catalytic activity for hydrogen evolution reaction (HER) was evaluated by linear sweep voltammetry and electrochemical impedance spectroscopy. In comparison with straightly electrodeposited black Pt film and forged Pt sheet electrodes, the HER current density has been significantly improved by the nanopillar-array architecture. The overpotential of HER at current density of 10 mA cm-2 at 26 °C is as low as 78 mV, lower than the black Pt film of 107 mV and the Pt sheet of 174 mV. The improvement of HER is ascribed to the low charge transfer resistance of the 3D electrode and the high desorption capability of hydrogen bubbles at the nanotips. Interestingly, the nanopillar-array 3D electrode has an optimal nanopillar length for HER. The mechanisms for the optimal nanopillar length were investigated here.     

Tailoring the hydrophilic and hydrophobic reaction fields of the electrode interface on single crystal Pt electrodes for hydrogen evolution/oxidation reactions

Interfacial hydrophobic/hydrophilic reaction fields significantly affect various reactions at the electrode surface. The hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR) have been investigated on single crystal Pt electrodes modified with hydrophobic/hydrophilic cations and anion-exchange copolymers in alkaline solutions. In alkali metal hydroxide solutions, Pt (110) exhibits the highest HER/HOR activity in the low-index planes of Pt. On the low-index planes of Pt, the hydrophilicity of the alkali metal cation in the supporting electrolyte activates the HER/HOR depending on its hydration energy. Hydrophilic cations at the interface facilitate the extraction of hydrogen from the hydrated water. The modification of anion-exchange copolymers with a hydrophobic skeleton on Pt (110) further enhanced the HER/HOR activity. The hydrogen bonding network formed around the hydrophobic species facilitated the mobility of water molecules and the OH⁻ as the reactant/product of the HER/HOR. Appropriately forming hydrophilic and hydrophobic reaction fields at the interface improved the HER/HOR activity.     

Palladium-coated polyaniline nanofiber electrode as an efficient electrocatalyst for hydrogen evolution reaction

In this study, polyaniline (PANI) with abundant protonated regions was used for the first time as a palladium (Pd) support for enhanced performance in hydrogen evolution reaction (HER). For this purpose, the hierarchical Pd@PANI nanofiber electrode was easily synthesized by electrochemical polymerization of aniline on Au followed by potential-controlled electrochemical deposition of Pd nanoclusters on the PANI. The reported catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. Linear sweep voltammetry analysis was performed to evaluate the HER performance. Ion transfer behavior was investigated using electrochemical impedance spectroscopy analysis. The electrochemical tests show that the Pd@PANI/Au electrode has a low overpotential of ～60 mV at 10 mA cm^?2 and a small Tafel slope of 35 mV dec^?1 for HER in acidic media, with high catalytic activity and stability. These features will make the Pd@PANI/Au a promising candidate as a high-performance electrocatalyst for HER applications.     

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.     

Pt/Fe-NF electrode with high double-layer capacitance for efficient hydrogen evolution reaction in alkaline media

The electrode with high catalytic activity, low hydrogen overpotential and low cost is desired for hydrogen evolution reaction (HER) via electrocatalytic water splitting. In this study, Pt/Fe-Ni foam (Pt/Fe-NF) electrode was synthesized via cathodic electrodeposition followed by impregnation deposition. Physical and electrochemical properties of Pt/Fe-NF, NF and Pt/NF electrodes were characterized by various techniques. The Pt/Fe-NF electrode exhibited better electrochemical activity for HER under alkaline condition than those of Pt/NF and NF electrodes, owing to the introduction of zero valences Pt and Fe onto the NF, and synergetic effect resulted from the formation of Fe-Ni alloy. Furthermore, Pt/Fe-NF electrode showed extremely high double-layer capacitance (69.1 mFcm^?2), suggesting high active sites for the Pt/Fe-NF. Tafel slope of Pt/Fe-NF was 59.9 mV dec^?1, indicating that the Volmer-Heyrovsky HER mechanism was the rate-limiting step. The Pt/Fe-NF electrode with great electrocatalytic activity is a promising electro-catalyst for industrial hydrogen production from alkaline electrolyte.     

Preparation of Pt dendrites on Poly(diallyldimethylammonium chloride)-functionalized reduced graphene oxide as an enhanced electrocatalyst for the hydrogen evolution reaction in alkaline media

Herein, we describe the synthesis of Pt dendrites with electrochemically active high-index planes on poly(diallyldimethylammonium chloride)-functionalized reduced graphene oxide (PFG) using a newly developed high-voltage electrochemical reduction (HVER) method. Subsequently, the catalytic activities of the prepared samples for the hydrogen evolution reaction (HER) in 1 M NaOH are characterized. The HVER method facilitates the preparation of nanoparticles in short reaction times. This method allows Pt particles to be formed by electron transfer from the cathode to a Pt precursor. Importantly, Pt particles deposited on PFG (Pt/PFG), prepared by the addition of PVP, are revealed to comprise both two- (2D) and three-dimensional (3D) dendrite structures, featuring abundant step and edge sites. The various factors affecting the morphology and the ratio of 2D to 3D dendrites of Pt were determined by TEM analysis. The ratio of 2D to 3D Pt dendrites depends on the amount of PVP employed and has a direct influence on the electrochemically active surface area (ECSA) and HER activity. Namely, the prepared Pt/PFG sample with the highest density of 2D Pt dendrites exhibits the highest HER activity due to its high ECSA. The performance of Pt/PFG13 (prepared keeping the PVP:Pt ratio as 13:1) was compared with that of commercial 40 wt% Pt/C, and the Pt/PFG13 sample exhibited superior current density (−424 mA/cm_geo² for Pt/PFG13 and –242 mA/cm_geo² for commercial 40 wt% Pt/C at −1.5 V vs. Hg/HgO; approximately 1.8 times higher) and catalytic stability, implying that these parameters are positively correlated with the increased number of step and edge sites.     

Effect of the thickness of nickel electrode with aligned porous structure on hydrogen evolution reaction

Seven nickel electrodes with aligned porous structure of different thicknesses (i.e., 100, 250, 400, 500, 600, 850, and 1100 μm) were fabricated via freeze casting, and the effect of the electrode thickness on hydrogen evolution reaction (HER) was experimentally studied. The polarization curves of the porous electrodes were obtained by linear sweep voltammetry (LSV) in a 1 M KOH solution. The results show that, in the lower current density zone, the overpotential decreases with the increasing thickness of the aligned porous electrode. At higher current density, the overpotential presents a relative complex variation with the electrode thickness. For a thicker porous electrode, its electrochemically active surface area (ECSA) undoubtedly increases. Nevertheless, its bubble removal ability decreases due to deeper porous channels, which adversely affects the HER performance. It is also found that while the aligned pore orientation of the electrode is parallel to gravity direction, the electrode with a thickness of 400 μm has a trade-off between the ECSA and bubble removal ability and shows optimal performance.     

Facile in-situ deposition of Pt nanoparticles on nano-pore stainless steel composite electrodes for high active hydrogen evolution reaction

Hydrogen is regarded as a clean and highly efficient renewable energy. The platinum catalytic electrode is widely used in hydrogen evolution reaction (HER), but it has affected its commercial application because of its high cost. Therefore, the study on cost-effective and high-active catalysts toward HER is required to realise large-scale hydrogen production. In this work, we present a novel Pt/NPSSF catalyst prepared by a one-step in-situ deposition of Pt precursor on a nano-porous stainless-steel film (NPSSF) substrate. The prepared catalyst was evaluated in acidic and alkaline conditions for its HER activities. The preliminary results demonstrate that the Pt/NPSSF electrodes have superior catalytic activity for HER. The hydrogen overpotential of Pt/NPSSF is ?70mV (RHE) in the alkaline solution, which is lower than the Pt electrode of ?184mV. At the same time, we also obtained ?71.2 mV of overpotential for the Pt/NPSSF electrode, which is similar to the ?73mV of Pt electrode in the acid solution. The Tafel graphs plotted from the LSV curves indicate the different HER mechanism in the alkaline and acid solution. The HER kinetics of the Pt/NPSSF were studied using EIS. Comparing Pt/NPSSF to Pt electrode, the multi-pore structures of NPSSF and the Pt nanoparticles active sites decrease the charge transfer-resistance for the HER process. The facile preparation, high efficiency and low value of the Pt/NPSSF composite electrodes demonstrate the promising applications in HER.     

The hydrogen evolution reaction on nickel-polyaniline composite electrodes

The electrolytic codeposition of nickel composite coatings with different amounts of polyaniline particles (PAni) was used to produce electrodes for the catalytic hydrogen evolution reaction (HER). The electrodes produced were imaged by scanning electron microscopy, and their catalytic activities for HER were determined by linear Tafel polarization and electrochemical impedance spectroscopy (EIS) in a 0.5 M H₂SO₄ solution. The electron micrographs showed that the amount of exposed polyaniline surface was directly related to the polyaniline concentration in the solution used for the electrolytic codeposition. The linear Tafel polarizations indicated that the HER was limited by the Volmer step, and the EIS measurements showed that the presence of PAni on the electrode surface affected the HER. Electrodes with higher composite contents exhibited enhanced catalytic activity.     

CuO/Pd composite photocathodes for photoelectrochemical hydrogen evolution reaction

CuO has been considered as a promising photocathodic material for photoelectrochemical (PEC) hydrogen evolution reaction (HER). In this work, CuO films were prepared by a facile and cost-effective method that involves solution synthesis, spin-coating and thermal treatment processes. The resulting CuO films had a monoclinic crystal structure with bandgap energy of 1.56 eV and a conduction band position of 3.73 eV below the vacuum level in borate buffer solution. The CuO films exhibited good PEC activity toward HER and the preparation conditions had great effect on the activity. The photoactivity of the CuO film decayed to approximately 19% of its original value after reaction for 10 h under illumination. The reduction of CuO to Cu₂O has been confirmed to be a parallel competitive reaction against HER. The mismatched band structure of the resulting CuO/Cu₂O heterojunction was believed to be the main cause of the decay of photoactivity. The photo-assisted electrodeposition method was developed to prepare CuO/Pd composite photocathode. The presence of Pd on CuO greatly increased the photocurrent especially at low overpotentials. In addition, the CuO/Pd composite exhibited significantly improved photostability compared to CuO. This work demonstrates the feasibility of increasing PEC activity and stability of CuO-based photocathodes by combining CuO with noble metal nanoparticles.     

The hydrogen evolution reaction on single crystal gold electrode

As one of the important candidate of power sources for the future, the research and production of hydrogen gas has a significant importance. In this article, the emphasis is on the influence of impurities on hydrogen evolution reaction, i.e., the influence of an addition of decacyclene, C₁₂H₃₅C₆H₄SO₄Na, CH₃CH₂OH, chromanone, H₂SO₄, HNO₃, 4,4′-biphenediol and 1,2,3,4-tetraphenyl-1,3-cyclopentadiene was studied by electrochemical impedance technique. The adsorption structure for some organics was measured by scanning tunneling spectroscopy techniques. Superstructure of adsorbed decacyclene on Au(111) surface was captured. The ordered adsorption structure of 4,4′-biphenyldiol on Au(111) and (100) was also observed. The addition of decacyclene has shown an opposite effects on hydrogen evolution for Au(111) and (100) surface, i.e., it inhibits the reaction at Au(100) but enhances the one at Au(111). The results show that the addition of C₁₂H₃₅C₆H₄SO₄Na and HNO₃, especially the latter, can improve the hydrogen evolution. In the article the adsorption structure and hydrogen evolution reaction have been studied in order to give some useful information about the relation between the adsorption structure and the properties. The purpose of this article is to attempt to find the relation between electrochemical performance and the adsorption structure, and to explore the effect of some additives.     

Kinetics of the hydrogen evolution reaction on NiMn graphite modified electrode

The mechanism and kinetics of the hydrogen evolution reaction (HER) on graphite modified with Ni and NiMn electrode (G/Ni and G/NiMn) in 0.1 M NaOH solution were studied using the methods of steady-state polarization, electrochemical impedance spectroscopy, cyclic voltammetry and open circuit potential transient. The addition of Mn to Ni significantly increases the catalytic activity in HER due to higher real surface area and higher intrinsic activity. The simulation of the data obtained from these methods, using nonlinear fitting procedure allowed us to determine the rate constants of Volmer, Heyrovsky and Tafel steps associated with the mentioned reaction. The kinetics results indicate that HER mechanism for G/NiMn electrode at low negative potentials is a serial combination of Volmer and parallel Tafel and Heyrovsky steps. At high negative potentials where the hydrogen coverage reaches its limiting value, a Tafel line with the slope of −125 mV dec⁻¹ is obtained. In this potential region the mechanism of the HER follows Volmer-Heyrovsky while the Tafel step has negligible contribution. Open circuit potential measurements for G/Ni and G/NiMn at different charging currents show that hydrogen absorption into the electrode material occurs.     

Fabrication of highly porous Pt coated nanostructured Cu-foam modified copper electrode and its enhanced catalytic ability for hydrogen evolution reaction

The nanoporous copper foam was prepared by electrochemical reduction of copper ion at the copper substrate. The as-prepared substrate was used as three-dimensional templates for preparation of Pt coated nanostructured Cu-foam by galvanic replacement of Cu with platinum by simply immersing the prepared nanoporous copper foam in a K₂PtCl₆ aqueous solution. The structure and nature of the fabricated Pt coated nanostructured Cu-foam was characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. Pt coated nanostructured Cu-foam modified copper electrode exhibited remarkable electrocatalytic activity for the hydrogen evolution reaction. The effect of electrodeposition time during Cu-foam formation on the kinetic constants for hydrogen evolution reaction was comparatively investigated.     

Aqueous substitution synthesis of platinum modified amorphous nickel hydroxide on nickel foam composite electrode for efficient and stable hydrogen evolution

Exploring highly active and stable electrocatalysts toward hydrogen evolution reaction (HER) is vital for the production of green energy and storage of intermittently renewable electrical energy. In this study, we fabricate Pt-modified Ni(OH)₂ on 3D nickel foam (Pt content: 1.5 wt %) via a one-step galvanic replacement reaction in aqueous solution to achieve a top performance of HER under alkaline conditions. It exhibits a negligible onset potential, a Tafel slope of 17 mV dec⁻¹, and overpotentials of 38, 114, and 203 mV to deliver 10, 50, and 100 mA cm⁻² current densities, respectively, which outperforms the commercial Pt/C and Pt sheet. Moreover, this catalyst shows enhanced durability towards HER, sustaining electrolysis at −20 mA cm⁻² for 4, 500 min in 1 M KOH with little degradation. Its good performances come from the synergism of flake-like Pt and amorphous Ni(OH)₂. This work provides not only a facile and easy scale-up approach to fabricate Pt−modified electrocatalysts with improved HER performance but also a new strategy to design self-supported high-performance hybrid materials of noble-metal and amorphous transitional metal hydroxides for sustainable energy conversion and storage.     

Optimizing the hydrogen evolution reaction by shrinking Pt amount in Pt-Ag/SiNW nanocomposites

In recent years, platinum-based catalysts are the most promising candidates for hydrogen evolution reaction (HER). Decrease of the Pt usage is an effective way to obtain low-cost hydrogen production. In order to achieve this goal, we synthesized Pt-Ag/SiNW composites with different dosages of Pt, using inexpensive Ag as a co-catalyst and SiNWs as carriers, and tested their catalytic performance in HER. The results showed that the optimal composition of Pt: Ag: Si = 4.1: 21.5: 74.4 in mass ratio. With such a low amount of Pt, the Pt-Ag/SiNW catalyst exhibited exciting HER performance, whose turnover frequency is 6.3H₂Pt^?1s^?1 at ?0.2 V vs. RHE, 2.7 times as large as that of 40 wt% Pt/C. This design greatly increased the utilization ratio of Pt, which may open a new way for preparation of other Pt-based catalysts.     

Monolayer palladium supported on molybdenum and tungsten carbide substrates as low-cost hydrogen evolution reaction (HER) electrocatalysts

Active and low-cost hydrogen evolution reaction (HER) electrocatalysts are needed to minimize capital costs associated with large-scale hydrogen production from water electrolysis. Catalysts based on monolayer (ML) amounts of precious metals supported on carbides are a promising concept for this purpose. In the current study Pd supported on tungsten carbide (WC) and molybdenum carbide (Mo₂C) were evaluated for HER activity. Carbide foils were synthesized using temperature programmed reaction of W or Mo in a CH₄/H₂ atmosphere. Physical vapor deposition was used to deposit Pd on WC or Mo₂C while X-ray Photoelectron Spectroscopy (XPS) was used to determine the Pd surface coverage. Linear sweep voltammetry and chronopotentiometry were used to evaluate the HER activity and electrochemical stability of the catalysts, demonstrating the possibility of using ML Pd on either WC or Mo₂C as active, stable and lower-cost HER catalysts.     

Enhancement of hydrogen evolution at cobalt-zinc deposited graphite electrode in alkaline solution

Thin Co layers were electrochemically deposited on a graphite electrode at different deposition current densities and thicknesses. After determining the best deposition conditions for hydrogen evolution (deposition current density and thickness), co-deposits of Co with Zn were prepared on the graphite electrode. The binary coatings prepared on the graphite electrode (CoZn) were etched in a concentrated alkaline solution (30% NaOH) to produce a porous and electrocatalytic surface suitable for use in the hydrogen evolution reaction (HER). After the leaching process, a low amount of Pt was deposited onto the etched CoZn deposit in order to further improve the catalytic activity of the electrode for the HER. The HER activity is assessed by recording cathodic current-potential curves, electrochemical impedance spectroscopy (EIS) and electrolysis techniques. Chemical composition of layers after alkaline leaching was determined by energy dispersive X-ray (EDX) analysis. The surface morphologies of coatings were investigated by scanning electron microscopy (SEM). It was found that, the HER activity of coatings depends on the metal ratio of Co and Zn, deposition current density and the thickness of coatings. The alkaline leached CoZn coating has a compact and porous structure as well as good electrocatalytic activity for the HER in alkaline media. Moreover, deposition of a low amount of Pt over the CoZn can further enhance its hydrogen evolution activity.     

Well-dispersed Pt nanodots interfaced with Ni(OH)2 on anodized nickel foam for efficient hydrogen evolution reaction

Hindered by price and scarcity, the exploitation of supported Pt-based electrocatalysts with Pt single atoms or Pt nanoclusters is an alternative way to decrease the dosage of Pt and improve the electrocatalytic performance for hydrogen evolution reaction (HER) of water splitting. The anodization technology is used to modify the surface of nickel foam (NF) to form the porous NiF₂ network structure. Then Pt nanodots interfaced with Ni(OH)₂ (Pt/Ni(OH)₂) hybrid on the anodized NF has been in-situ synthesized by a simple hydrothermal decomposition method. Results show that Pt nanodots on the substrate have good dispersion with the average size of 3 nm, and the Pt loading is only 0.229 mg cm⁻². The prepared electrode exhibits the low overpotentials of 25.9 mV and 211 mV at the current densities of 10 and 100 mA cm⁻², respectively, a small Tafel slope of 37.6 mV dec⁻¹, and the excellent durability for HER. The porous network nanostructure of Pt/Ni(OH)₂ hybrid, the large electrochemical surface area, the fast facilitated electron transport capability, and the firm adhesion of Pt nanodots with the anodized NF substrate contribute to the remarkable performance towards HER.     

In-situ anion exchange synthesis of copper selenide electrode as electrocatalyst for hydrogen evolution reaction

Efficient and robust Earth-abundant catalysts for hydrogen evolution reaction (HER) is one of the key components for clean energy technologies aimed at reducing future carbon emissions. Here, an in-situ anion exchange approach to prepare hierarchical nanostructures consisting of ultrathin Cu_2-xSe nanosheet is reported. With the aid of the selenylation process and the hierarchical ultrathin nanostructure, the nanostructured Cu_2-xSe/Cu foam electrode achieved considerably enhanced HER performance with a large geometric current density of ?100 mA cm^?2 at a small overpotential of 313 mV and outstanding long-term operational stability. Significant improvement of electrocatalytic activity for Cu_2-xSe catalyst could be attributed to the promoted mass diffusion/transfer properties, which results from its special structural feature. Meanwhile, the overpotential associated with the catalyst/substrate interface could be effectively eliminated due to the self-supported construction. We believe that this work will lead towards the further development of Cu-based chalcogenides for applications in electrocatalysis and energy conversion.     

Design of advanced self-supported electrode by surface modification of copper foam with transition metals for efficient hydrogen evolution reaction

Electrocatalytic water splitting is one of the most favorable methods for industrial-scale hydrogen production, but high cost and scarcity of commercially available noble metals restrict its application for hydrogen evolution reaction (HER). It is challenging to develop efficient non-noble metal-based electrocatalysts for HER. Herein, a Ni–Cr was doped on Copper foam (CF) substrate by adopting a simple annealing process. The high electrocatalytic efficiency for HER was achieved with Ni–Cr@CF electrode in strong basic medium with a lower overpotential of 144 mV to gain a current density of 10 mA cm⁻² with a small Tafel slope of 88 mV dec⁻¹. After surface modification, the CF substrate exhibits that the entire surface was uniformly covered with Ni–Cr species ensuring the fast reaction kinetics due to the efficient electron transfer process between the substrate and active catalyst. Moreover, the Ni–Cr@CF electrode exhibits excellent stability up to 2000 cycles under the strong basic medium.