Sonoactivated polycrystalline Ni electrodes for alkaline oxygen evolution reaction

The development of cost-effective and active water-splitting electrocatalysts is an essential step toward the realization of sustainable energy. Its success requires an intensive improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. In this work, we designed a facile and one-route strategy to activate the surface of metallic nickel (Ni) for the OER in alkaline media by ultrasound (24 kHz, 44 W, 60% acoustic amplitude, ultrasonic horn). Sonoactivated Ni showed enhanced OER activity with a much lower potential at + 10 mA cm⁻² of + 1.594 V vs. RHE after 30 min ultrasonic treatment compared to + 1.617 V vs. RHE before ultrasonication. In addition, lower charge transfer resistance of 11.1 Ω was observed for sonoactivated Ni as compared to 98.5 Ω for non-sonoactivated Ni. In our conditions, ultrasound did not greatly affect the electrochemical surface area (A_ecsa) and Tafel slopes however, the enhancement of OER activity can be due to the formation of free OH^• radicals resulting from cavitation bubbles collapsing at the electrode/electrolyte interface.     

A facile sonochemical route for the synthesis of MoS2/Pd composites for highly efficient oxygen reduction reaction

For the alkaline fuel cell cathode reaction, it is very essential to develop novel catalysts with superior catalytic properties. Here, we report the synthesis of highly active and stable MoS₂/Pd composites for the oxygen reduction reaction (ORR), via a simple, eco-friendly sonochemical method. The bulk MoS₂ was first transformed into single and few layers MoS₂ nanosheets through ultrasonic exfoliation. Then the exfoliated MoS₂ nanosheets served as supporting materials for the nucleation and further in-situ growth of Pd nanoparticles to form MoS₂/Pd composites via ultrasonic irradiation. Cyclic voltammetry and rotating disk voltammetry measurements demonstrate that as-prepared MoS₂/Pd composites which provides a direct four-electron pathway for the ORR, have better electrocatalytic activity, long-term operation stability than commercial Pt/C catalyst. We expect that the present work would provide a promising strategy for the development of efficient oxygen reduction electrocatalyst. In addition, this study can also be extended to the preparation of other hybrid with desirable morphologies and functions.     

Ultrasound-assisted transformation from waste biomass to efficient carbon-based metal-free pH-universal oxygen reduction reaction electrocatalysts

Efficient carbon-based nitrogen-doped electrocatalysts derived from waste biomass are regarded as a promising alternative to noble metal catalysts for oxygen reduction reaction (ORR), which is crucial to fuel cell performance. Here, coconut palm leaves are employed as the carbon source and a series of nitrogen-doped porous carbons were prepared by virtue of a facile and mild ultrasound-assisted method. The obtained carbon material (ANDC-900-10) conveys excellent pH-universal catalytic activity with onset potentials (E_onset) of 1.01, 0.91 and 0.84 V vs. RHE, half-wave potentials (E_1/2) of 0.87, 0.74 and 0.66 V vs. RHE and limiting current densities (J_L) of 5.50, 5.45 and 4.97 mA cm⁻² in alkaline, neutral and acidic electrolytes, respectively, prevailing over the commercial Pt/C catalyst and, what's more, ANDC-900-10 displays preeminent methanol crossover resistance and long-term stability in the broad pH range (0–13), thanks to its abundant hierarchical nanopores as well as effective nitrogen doping with high-density pyridinic-N and graphitic-N. This work provides sonochemical insight for underpinning the eco-friendly approach to rationally designing versatile metal-free carbon-based catalysts toward the ORR at various pH levels.     

Exploration of bimetallic Pt-Pd/C nanoparticles as an electrocatalyst for oxygen reduction reaction

In this study, carbon supported Pt and Pt-Pd were synthesized as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs). Pt and Pt-Pd nanoparticles have been synthesized by reduction of metal precursors in presence of NaBH₄. Various techniques such as X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) were utilized to study the prepared samples. Furthermore, electrochemical properties of the prepared samples were evaluated from cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The results showed, the crystallite size of electrocatalysts (Pt and Pt-Pd) is below 10 nm. The higher catalytic activity was detected for Pt-Pd/C electrocatalyst for oxygen reduction reaction (ORR). In addition, it is believed that the better performance of electrocatalyst is related to the synergic effect between Pt and Pd nanoparticles, weakening of the OO bond on Pd-modified Pt nanoparticles in ORR, uniform dispersion of Pd and Pt on the carbon support and higher electrochemical active surface area (EAS) of Pt-Pd/C electrocatalyst.     

First-principles study on Sb-doped SnS2 as a low cost and non-toxic absorber for intermediate band solar cell

Tin disulfide has attracted much attention on solar cell study due to its excellent optoelectronic properties in addition to just containing low-cost and non-toxic elements. Based on the HSE06-hybrid function calculations combined with Grimme's dispersion-correction method, a half-filled and delocalized intermediate band(IB) is presented in the main band gap of SnS₂ after partially Sb substituting on Sn site, which is made of the antibonding states of Sb-s and S-p states. Three-photon absorption can be realized in the doped sample and its corresponding absorption coefficient is enhanced at the visible light region thanks to the isolated and half-filled IB above the original valence band. Furthermore, Sb_Sn always has the lowest formation energy than other Sb-related defects (i.e. Sb_S and Sb_i) based on the defect formation energy calculations. Therefore, Sb-doped SnS₂ is suggested as a promising candidate for the absorber of intermediate band solar cell.     

Laser fragmentation in liquid synthesis of novel palladium-sulfur compound nanoparticles as efficient electrocatalysts for hydrogen evolution reaction

One promising way to tune the physicochemical properties of materials and optimize their performance in various potential applications is to engineer material structures at the atomic level. As is well known, the performance of Pd-based catalysts has long been constrained by surface contamination and their single structure. Here, we employed an unadulterated top-down synthesis method, known as laser fragmentation in liquid (LFL), to modify pristine PdPS crystals and obtained a kind of metastable palladium-sulfur compound nanoparticles (LFL-PdS NPs) as a highly efficient electrocatalyst for hydrogen evolution reaction (HER). Laser fragmentation of the layered PdPS crystal led to a structural reorganization at the atomic level and resulted in the formation of uniform metastable LFL-PdS NPs. Noteworthy, the LFL-PdS NPs show excellent electrocatalytic HER performance and stability in acidic media, with an overpotential of -66 mV at 10 mA· cm^-2, the Tafel slope of 42 mV· dec^-1. The combined catalytic performances of our LFL-PdS NPs are comparable to the Pt/C catalyst for HER. This work provides a top-down synthesis strategy as a promising approach to design highly active metastable metal composite electrocatalysts for sustainable energy applications.     

Ultrasound assisted synthesis of highly active nanoflower-like CoMoS4 electrocatalyst for oxygen and hydrogen evolution reactions

Rapid technological development requires sustainable, pure, and clean energy systems, such as hydrogen energy. It is difficult to fabricate efficient, highly active, and inexpensive electrocatalysts for the overall water splitting reaction: the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The present research work deals with a simple hydrothermal synthesis route assisted with ultrasound that was used to fabricate a 3D nanoflower-like porous CoMoS₄ electrocatalyst. A symmetric electrolyzer cell was fabricated using a CoMoS₄ electrode as both the anode and cathode, with a cell voltage of 1.51 V, to obtain a current density of 10 mA/cm². Low overpotentials were observed for the CoMoS₄ electrode (250 mV for OER and 141 mV for HER) at a current density of 10 mA/cm².     

Ultrasonic-assisted hydrothermal synthesis of cobalt oxide/nitrogen-doped graphene oxide hybrid as oxygen reduction reaction catalyst for Al-air battery

A persistent ultrasound-assisted hydrothermal method has been developed to prepare cobalt oxide incorporated nitrogen-doped graphene (Co₃O₄/N-GO) hybrids. The electrochemical behaviors and catalytic activity of the prepared hybrids have been systematically investigated as cathode materials for Al-air battery. The results show that ultrasonication can promote the yield ratio of Co₃O₄ from 63.1% to 70.6%. The prepared Co₃O₄/N-GO hybrid with ultrasonication exhibits better ORR activity over that without ultrasonication. The assembled Al-air battery using the ultrasonicated Co₃O₄/N-GO hybrid exhibited an average working voltage of 1.02 V in 4 M KOH electrolyte at 60 mA∙cm⁻², approximately 60 mV higher than that using hybrid without ultrasonication. This should be attributed to large number density of fine Co₃O₄ particles growing on the dispersed GO sheets under the persistent ultrasonication. The related ultrasonic mechanism has been discussed in details.     

One-step ultrasonic synthesis of Co/Ni-catecholates for improved performance in oxygen reduction reaction

The inherent periodically arranged M−N_X, M−S_X and M−O_X units (M are usually Fe, Co, Ni, etc.) in metal–organic frameworks (MOFs) can be promising active centers in electrocatalysis. In previous studies, MOFs were usually constructed by energy-consuming hydro- or solvo-thermal reactions. Ultrasonic synthesis is a rapid and environment-friendly technique when envisaging MOFs’ industrial applications. In addition, different synthetic pathways for MOFs may lead to difference in their microstructure, resulting in different electrocatalytic performance. Nevertheless, only a handful of MOFs were successfully prepared by ultrasonic synthesis and few were applied in electrochemical catalysis. Herein, we constructed Ni/Co-catecholates (Ni/Co-CATs) synthesized by one-step ultrasonic method (250 W, 40 KHz, 25 W/L, Ultrasonic clearing machine) and compared their performance in oxygen reduction reaction (ORR) with that of Ni/Co-CATs synthesized by hydrothermal method. Ni-CAT and Co-CAT prepared by ultrasonic showed the half-wave potential of −0.196 V and −0.116 V (vs. Ag/AgCl), respectively. The potentials were more positive than those prepared by hydro-thermal method. And they showed excellent electrochemical stability in neutral solution. The latter was only 32 mV lower than that of commercial Pt/C. The improved performance in ORR was attributed to higher specific surface area and mesopore volume as well as more structural defects generated in the ultrasonic synthesis process, which could facilitate their exposure of electrocatalytic active sites and their mass transport. This work gives some perspective into cost-effective synthetic strategies of efficient MOFs-based electrocatalysts.     

Dealloyed PtCu catalyst as an efficient electrocatalyst in oxygen reduction reaction

Pt-transition metal alloy catalysts with an active Pt surface have exceptional properties for use in oxygen electro-reduction reactions in fuel cells. Herein, we report the simple synthesis of dealloyed PtCu catalysts and their catalytic performance in oxygen reduction. The dealloyed PtCu catalysts consisted of a Pt-enriched shell with a Pt–Cu alloy core and were synthesized through a chemical co-reduction process followed by thermal annealing and chemical dealloying. During synthesis, thermal annealing leads to a high degree of formation of PtCu alloy particles (e.g., PtCu or PtCu₃), and chemical dealloying causes selective dissolution of unstable Cu species from the surface layers of the PtCu alloy particles, resulting in a PtCu alloy@Pt-enriched surface core–shell configuration. Our PtCu₃/C catalyst exhibits a great improvement in the oxygen reduction reaction with a mass activity of 0.501 A/mg_Pt, which is 2.24 times greater than that of a commercial Pt catalyst. In this article, the synthesis details, characteristics and performance improvements in ORR of chemically dealloyed PtCu catalysts are systemically explained.     

Nitrogen doped carbon nano-onions as efficient and robust electrocatalysts for oxygen reduction reactions

We investigated synthesis and electrocatalytic performance of metal-free, nitrogen-doped carbon nano-onions (N-CNOs) for oxygen reduction reactions in alkaline electrolyte. N-CNOs were prepared by chemical oxidation of nanodiamond-derived carbon nano-onions (ox-CNOs), followed by thermal annealing with urea under the flow of argon gas. The chemical oxidation step was critical to successfully internalize nitrogen atoms into carbon network. Morphology, microstructure, and chemical states of carbon nano-onions (CNOs), ox-CNOs, and N-CNOs were characterized by transmission electron microscopy (TEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Electrocatalytic activity of pristine and modified CNOs was characterized by a series of electrochemical measurements. Electrochemical characterizations were done with thin film electrodes of CNOs mounted on a glassy carbon disk. Compared to CNOs and ox-CNOs, N-CNOs showed remarkably enhanced electron-transfer kinetics with the 4-electron transfer as a dominant reaction pathway. Overall, N-CNOs exhibited electrochemical characteristics comparable to commercial Pt/C catalysts.     

Direct pyrolysis and ultrasound assisted preparation of N,S co-doped graphene/Fe3C nanocomposite as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions

Bifunctional electrocatalysts to enable efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for fabricating high performance metal–air batteries and fuel cells. Here, a defect rich nitrogen and sulfur co-doped graphene/iron carbide (NS-GR/Fe₃C) nanocomposite as an electrocatalyst for ORR and OER is demonstrated. An ink of NS-GR/Fe₃C is developed by homogeneously dispersing the catalyst in a Nafion containing solvent mixture using an ultrasonication bath (Model-DC150H; power − 150 W; frequency − 40 kHz). The ultrasonically prepared ink is used for preparing the electrode for electrochemical studies. In the case of ORR, the positive half-wave potential displayed by NS-GR/Fe₃C is 0.859 V (vs. RHE) and for the OER, onset potential is 1.489 V (vs. RHE) with enhanced current density. The optimized NS–GR/Fe₃C electrode exhibited excellent ORR/OER bifunctional activities, high methanol tolerance and excellent long-term cycling stability in an alkaline medium. The observed onset potential for NS–GR/Fe₃C electrocatalyst is comparable with the commercial noble metal catalyst, thereby revealing one of the best low-cost alternative air–cathode catalysts for the energy conversion and storage application.     

Composite Nanoarchitectonics with iron nickel bimetallic nanoparticles and carbon composite for efficient electrocatalysis in hydrogen evolution reaction

The poor efficiency and stability of cost-effective metal compounds are major hurdles to substitute expensive metal-based nanomaterials for the hydrogen evolution reaction (HER). As a result, new concepts and tactics for developing electrocatalysts based on earth-abundant elements must be developed. We present iron-nickel alloy nanoparticles that are supported with carbon (FeNi@C) to improve HER performance in alkaline conditions. FeNi particle was supported on Trimesic acid (TMA) based carbon. In particular, the high conductivity of the carbon and a large number of catalytically active sites in the FeNi demonstrated a synergistic effect, making the hybrid structure a good choice for HER catalyst. Moreover, the physicochemical interaction between the carbon and FeNi metal enhanced the electrocatalytic performance and resulted in achieving 10 mA/cm² current density at 190 mV overpotential with 15 h chronopotential cycling, proving the possibility for replacing costly Pt-based catalysts.     

B,N-codoped 3D micro-/mesoporous carbon nanofibers web as efficient metal-free catalysts for oxygen reduction

B, N-codoped carbon nanofibers were massively prepared by heat treatment of electrospun carbon nanofibers with the mixture of boric acid/urea in N₂ (BNC_f-N) and subsequently activated in NH₃ (BNC_f-NA). The directly electrospun self-standing 3D non woven structure with void spaces between each fiber facilitates the mass transport of reactant and resulted molecules. Further NH₃ activation gives BNC_f-NA a high surface area of 306.3 m² g⁻¹ with micro/mesoporous structure, providing abundant passageway for proton transfer. Simultaneously, NH₃ activation also realizes the optimization of surface functionalities, such as more B–N–C and pyridinic-N. These intriguing features render BNC_f-NA excellent catalytic behavior with nearly four-electron oxygen reduction reaction (ORR) process in alkaline media, especially much better stability and methanol tolerance than the commercial Pt/C catalyst. Our work provides a large-scale preparation method for efficient metal-free catalysts toward ORR, thus further intensifying the commercial application of fuel cells.     

Catalytic activity of carbon-supported iridium oxide for oxygen reduction reaction as a Pt-free catalyst in polymer electrolyte fuel cell

Iridium oxide supported on Vulcan XC-72 carbon black (IrO₂/C) as a cathode catalyst for polymer electrolyte fuel cell (PEFC) has been characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) measurement. The IrO₂ particles were 8-160 nm in diameter. The oxygen electroreduction activity was studied by cyclic voltammetry (CV). It was found that IrO₂/C had high oxygen reduction reaction (ORR) activity. The performance of the membrane electrode assemble (MEA) was also tested in a single PEFC and showed that IrO₂/C catalyst would be potential candidates for use as cathode catalyst in PEFC.     

铜纳米阵列高效电解水产氧催化剂的制备

本文报道了一种利用简单的两步牺牲模板法,在泡沫铜基底表面完成了三维氧化铜纳米晶阵列的生长. 氧化铜纳米晶阵列具有良好的导电性,稳定性,在碱性溶液中有着优秀的电解水产氧催化性能. 氧化铜纳米晶阵列催化水的电化学氧化只需400 mV的过电势即可达到100 mA/cm²的电流密度,与其它铜基电解水产氧催化剂以及贵金属IrO₂相比都有着明显的优势. 氧化铜纳米晶阵列在270 mA/cm²左右的工作电流下连续工作10 h依然可以保持良好的稳定性,是相同的工作电压下IrO₂工作电流的10倍(约25 mA/cm²).     

Three-dimensional flower-like NiS2/MoS2 assembly of randomly oriented nanoplate for enhanced hydrogen evolution reaction

The continually worsening energy crisis has stimulated research into energy conversion technology to produce pure hydrogen, H₂. Transition metal-based compounds have attracted great attention as electrocatalysts for hydrogen evolution reaction (HER) as alternatives to commercial, high-cost, and scarce noble metal-based catalysts. In this work, a 3D flower-like NiS₂/MoS₂ is synthesized with the advantages of a three-dimensional (3D) morphology and the compositing of different metal compounds, thus leading to enhanced electrocatalytic performance. The structure of 3D flower-like NiS₂/MoS₂ augments the specific surface areas resulting from nanoplate assemblies as well as the heterointerface ascribed to two different phases of NiS₂ and MoS₂. These characteristics are confirmed by electrocatalytic measurements of the lower overpotential of 165 mV at 10 mA/cm² with high charge transfer ability, thus demonstrating the structure's potential for advanced electrocatalysts for the HER.     

High-throughput screening of binary catalysts for oxygen electroreduction

A series of Pt based and non-Pt catalysts for proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC) have been evaluated towards oxygen reduction, by high-throughput optical screening. Fluorescein was first used as pH indicator for detecting pH change of the electrolyte in the vicinity of cathode caused by oxygen reduction. Arrays of catalyst spot comprised of binary catalysts and pure Pt were prepared by using robotic micro-dispenser. The analysis of fluorescence images has showed that some of Pt based catalysts including PtBi, PtCu, PtSe, PtTe and PtIr, as well as RuFe, as a non-Pt catalyst, exhibited higher activities and methanol tolerance than pure Pt. Moreover, acceptable stability of these catalysts at high potential in acid environment suits them to the requirements of cathode catalyst in PEMFC or DMFC.     

Facile preparation of SnC2O4 nanowires for anode materials of a Li ion battery

A simple method of creating densely-packed nanostructures of functional metal oxides is attractive, but it has always been a challenge. Here, we synthesize well-distributed nanostructures of Sn complexes (SnC₂O₄ and SnO₂) via a simple chemical anodization technique followed by annealing. Chemical anodization of Sn surface in oxalic acid, using various organic solvents, provides one-dimensional nanostructures of SnC₂O₄. Length and packing density were precisely controlled by several parameters: solubility of oxalic acid, dielectric constant of organic solvents, and the ion transfer of proton and oxalate anion. Further thermal decomposition converts the SnC₂O₄ nanowires into SnO₂ nanowires, maintaining the nanostructure form in the process. In addition, we expect that the mixture of SnC₂O₄ and SnO₂ nanowires synthesized by this approach might be potential alternative anode materials for prompt charging and discharging Li ion batteries.     

Facile synthesis of porous CuS film as a high efficient counter electrode for quantum-dot-sensitized solar cells

In this paper, porous CuS film has been successfully prepared by a facile method and employed as a counter electrode (CE) in quantum-dot-sensitized solar cells (QDSSCs) for its highest catalytic activity. This CuS thin film was deposited on FTO substrate via spin coating process which is simple to operate, and its electrochemical properties were further studied by EIS and Tafel measurement. With the cycling time of depositing CuS up to 8, it displays high electrocatalytic activity toward polysulfide reduction, rationalizing the improved QDSSCs performance. Using the CdS/CdSe-sensitized QDSSCs, the cells exhibit improved short-circuit photocurrent density (J _sc) and fill factor (FF), achieving solar cell conversion efficiency (η) as high as 5.60 % under AM 1.5 illumination of 100 mW cm^?2. This work provides a novel and simple method for the preparation of CEs, which could be utilized in other metal sulfides CEs for QDSSCs.