Electrocatalytic Applications Research Articles

Effect of vibrational resonances and dynamic polarizability on the Raman spectrum of furfural: A vibrational coupled cluster study

The Raman spectrum of furfural is computed and analyzed using the Vibrational Coupled Cluster Method (VCCM). Furfural has immense applications in organic synthesis, electrocatalysis and energy conversion process. The experimental Raman spectrum of furfural is congested and broad, even in the medium energy regions like C-C stretching and CO stretching regions. We extensively analyze the Fermi and higher quanta resonance effects on the Raman spectrum by examining the VCCM wavefunctions. In addition, a systematic study on the effect of incident frequency on the anharmonic Raman activity is carried out by comparing the results with incident wavelengths 325.0 nm and 632.8 nm against static polarizability.

Metal-Assisted Chemical etching for the direct synthesis of bimetallic Cu-Pd nanoparticles on silicon

An original study is presented for the synthesis of Cu100-xPdx nanoparticles directly on silicon by Metal Assisted Chemical Etching (MACE). CuPd is chosen as a representative bimetallic system on account of its interest and potential applications in catalysis and electrocatalysis, among others. The proposed methodology allows precise control of the nanoparticle bimetallic composition and structure. Thus, we demonstrate that Cu100-xPdx solid solutions and phase-separated nanoparticles can be synthesized at will by simply changing the deposition conditions. In-depth physical characterization of the synthesized material (structure, morphology, composition, oxidation state and d-band center position) is carried out by XRD, SEM-EDX and XPS. Finally, band bending simulations at the nanoscale in combination with electrochemical measurements help to interpret some of the peculiarities of the Pd, Cu and Cu100-xPdx deposits. The new method can be easily implemented, used for various silicon substrate geometries and extended to any bimetallic system whose metals are suitable for MACE of silicon.

Fe regulating Ni3S2/ZrCoFe-LDH@NF heterojunction catalysts for overall water splitting

With the continuous depletion of traditional energy sources, the development of sustainable energy sources has become one of the important tasks today. A two-step synthesis method was employed to construct Ni3S2/ZrCoFe-LDH@NF heterostructured electrocatalysts on nickel foam (NF) in situ. X-ray diffractometer, scanning electron microscope, transmission electron microscope, and X-ray electron spectroscopy were employed to characterize the Ni3S2/ZrCoFe-LDH@NF heterostructure, and the hydrogen-extraction reaction (HER), oxygen-extraction reaction (OER) and total hydrolysis properties of this electrocatalyst were tested in 1 mol·L−1 KOH electrolyte. It is shown that Ni3S2/ZrCoFe-LDH@NF is a lamellar stacked heterostructure with an overpotential of 330 mV and a Tafel slope of 90.9 mV·dec−1 at a current density of 100 mA·cm−2 in the OER reaction and 159.2 mV at a current density of 10 mA·cm−2 in the HER reaction. The Tafel slope is 96 mV·dec−1, and the catalyst exhibits good structural stability in the 100 h total hydrolysis stability test. The successful construction of this heterostructured electrocatalyst provides a good idea and research basis for the subsequent heterojunction and its application in electrocatalysis.

Enhancing oxygen evolution functionality through anodization and nitridation of compositionally complex alloy

Compositionally complex materials (CCMs) have recently attracted great interest in electrocatalytic applications. To date, very few materials were systematically developed and tested due to the highly difficult preparation of high-surface-area CCMs. In this work, a surface of a compositionally complex FeCoNiCuZn alloy (CCA) was nitridated with subsequent anodization leading to morphological and compositional modifications. Notably, the electrochemical surface area and surface roughness as well as the electrocatalytic activity of the anodized material exhibit significant enhancement. Oxygen evolution reaction (OER) activity by the anodized CCN (CCN–AO) proceeds with remarkably small overpotential (233 mV) at 10 mA cm−2 in 1 M KOH. Experimental characterization indicates that the oxidation state of Co plays a critical role in the Fe–Co–Ni electrocatalyst. The developed approach and design strategy open up immense prospects in the preparation of a new, affordable, scalable and effective type of complex and high-performance electrocatalytic electrodes with tunable properties.

Empowering the Water Oxidation Activity of the Bimetallic Metal-Organic Framework by Annexing Gold Nanoparticles over the Catalytic Surface.

Electrocatalytic water splitting to an anodic oxygen evolution reaction (OER) and a cathodic hydrogen evolution reaction (HER) is believed to be the most important application for sustainable hydrogen generation. Being a four-electron, four-proton transfer process, the OER plays the main obstacle for the same. Therefore, designing an effective electrocatalyst to minimize the activation energy barrier for the OER is a research topic of prime importance. The metal-organic framework (MOF) with a highly porous network is considered an appropriate candidate for the OER in alkaline conditions. Apart from several MOFs, the bimetallic one has an advantageous electrocatalytic performance due to the synergistic electronic interaction between two metal ions. However, most bimetallic MOFs have an obstacle to electrocatalytic application due to their low conductive nature, and therefore, they possess a barrier for charge transfer kinetics at the interface. Surface functionalization via various nanoparticles (NPs) is believed to be the most effective strategy for nullifying the conductive issue. In this work, we have designed a CoNi-based bimetallic MOF that was surface-functionalized by Au NPs (Au@CoNi-Bpy-BTC) for the OER under alkaline conditions. Au@CoNi-Bpy-BTC required an overpotential of just 330 mV, which is 56 mV lower as compared to the pristine MOF. Impedance analysis confirms an improved conductivity and charge transfer at the interface, where Au@CoNi-Bpy-BTC possesses a lower Rct value than CoNi-Bpy-BTC materials. Moreover, the Au-decorated MOF shows an 8.5 times increase in the TOF value compared to the pristine MOF. Therefore, this noble strategy toward the surface functionalization of MOFs via noble metal NPs is believed to be the most effective strategy for developing effective electrocatalysts for electrocatalytic application in energy-related fields. Overall, this report displays an exceptional correlation between the decorated NPs over the MOF surface, which can regulate the OER activity, as confirmed by experimental analysis.

Atomically precise Au15Ag23 nanoclusters co-protected by alkynyl and bromine: Structure analysis and electrocatalytic application toward overall water splitting

We report the structure analysis and electrocatalytic application toward overall water splitting of atomically precise Au15Ag23(tBuC ≡ C)18Br6 nanoclusters (Au15Ag23 in short). Au15Ag23 possesses a triple-layered core-shell-shell metal core structure of Au6@Au6Ag23@Au3, with the core centre being a tetragonal bipyramidal Au6 structure unit, and the outer layer of one Ag atom linked with two alkynyl ligands to form a linear structural motif covering the surface of the metal nucleus. Au15Ag23 is a superatom with 14 free electrons and it displays a unique absorption profile. Remarkably, the Au15Ag23 catalyst exhibits excellent electrocatalytic properties in hydrogen evolution reaction (HER), manifested by a low overpotential of 125 mV at 10 mA cm−2 and a negligible current decrease for 16 h in 0.5 M H2SO4, while the Au15Ag23/NiFe-LDH catalyst demonstrates outstanding electrocatalytic performance in oxygen evolution reaction (OER), evidenced by an ultralow overpotential of 250 mV at 10 mA cm−2 and a ∼5% current decrease for 30 h in 1.0 M KOH. Such promoting effect is ascribed by the electron transfer from NiFe-LDH to the Au15Ag23 clusters, which results in generating high valent Fe species as active sites. When using the two catalysts for overall water splitting (OWS), only 1.51 V was required to achieve a current density of 10 mA cm−2, and it performed well in the 50 h's stability test. This study enriches the family member of alkynyl-protected AuAg bimetallic nanoclusters, and further highlights the dual functionalities (catalyzing HER and promoting OER) that metal nanoclusters can make contribution for electrochemical energy conversion and beyond.

Enhanced Interband Transition in FeCoNiAlTi High‐Entropy Alloy for Ultrafast Nonlinear Optical Applications

AbstractHigh‐entropy alloys (HEAs) possess superior mechanical, thermal, and electronic properties, which attract great interest in the fields of photothermal, electrocatalysis, and magnetic applications. Herein, the nonlinear optical properties of FeCoNiAlTi HEA with a large specific surface area for the first time is investigated. Owing to the strong d–d interaction, the interband transition near the Fermi level could be enhanced in HEAs, leading to broadband optical absorption. Excitation with the picosecond laser source, the FeCoNiAlTi HEA possesses saturable absorption with a large modulation depth of 7.61% and 30.47% at 1 and 1.5 µm, respectively. Furthermore, at the higher excitation level at 1.5 µm, the saturable absorber exhibits a typical reverse saturable absorption property. Subsequently, the FeCoNiAlTi HEA on the tapered fiber first serves as the saturable absorber in the Yb‐doped fiber laser and the Er‐doped fiber laser, leading to the noise‐like pulses at 1 µm, and the stable Q‐switching, conventional soliton, and dissipative soliton resonance mode‐locking operations at 1.5 µm. This work confirms that the enhanced saturable absorption in HEAs can endow the high‐performance ultrashort pulse generation.

Synthesis of Conductive MOFs and Their Electrochemical Application.

Conductive metal-organic frameworks (MOFs) are a type of porous material. It consists of metal ions coordinated with highly conjugated organic ligands. The high density of carriers and orbital overlap contribute to the amazing conductivity. Additionally, conductive MOFs inherit the advantages of large specific surface area, structural diversity, and adjustable pore size from MOFs. These excellent properties have attracted many researchers to explore controllable synthesis and electrochemical applications over the past decade. This work provides an overview of the recent advances in the synthesis strategies of conductive MOFs and highlights their applications in electrocatalysis, supercapacitors, sensors, and batteries. Finally, the challenges faced by the synthesis and application of conductive MOFs are discussed, as well as the views on promising solutions for them are presented.

Direct synthesis of N, S co‐doped graphynes via copolymerization strategy for electrocatalytic application

AbstractGraphynes (GYs) are a novel set of carbon allotropes with high potential as future catalytic electrodes for oxygen reduction reactions because of their unique physical and chemical properties. In recent years, a number of heteroatom‐doped graphdiyne (GDYs) based electrocatalysts have been developed. However, the development of GYs has made slow progress due to their limited synthetic strategies. Here, the first case of nitrogen and sulfur co‐doped graphynes (NS‐GYs) synthesized through the copolymerization between hydrogen‐deficient heterocyclic aromatic monomers via the Sonogashira–Hagihara cross‐coupling reaction is reported. The NS‐GYs exhibit abundant porosity after heat treatment with large specific area and high heteroatom content for use as potential electrocatalysts. In addition, NS‐GY‐3‐800 with the best electrocatalytic performance shows excellent power density and stability in Zn‐air batteries.

Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites.

Thiomolybdates are molecular molybdenum-sulfide clusters formed from Mo centers and sulfur-based ligands. For decades, they have attracted the interest of synthetic chemists due to their unique structures and their relevance in biological systems, e.g., as reactive sites in enzymes. More recently, thiomolybdates are explored from the catalytic point of view and applied as homogeneous and molecular mimics of heterogeneous molybdenum sulfide catalysts. This review summarizes prominent examples of thiomolybdate-based electro- and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. Active sites of thiomolybdates relevant for the hydrogen evolution reaction are examined, aiming to shed light on the link between cluster structure and performance. The shift from solution-phase to surface-supported thiomolybdates is discussed with a focus on applications in electrocatalysis and photocatalysis. The outlook highlights current trends and emerging areas of thiomolybdate research, ending with a summary of challenges and key takeaway messages based on the state-of-the-art research.

2023 Colin Garfield Fink Postdoctoral Summer Fellowship – Summary Report: The Effect of Electrochemical Hydrogen Production and Storage in Ti3C2T x MXene on Cell Pressure

Hydrogen is a clean fuel that can power vehicles with high efficiency and produce water as the only byproduct. However, hydrogen technologies face challenges that include low volumetric storage capacity. One way to increase volumetric capacity is to store hydrogen in solid state materials. MXenes represent the fastest-growing family of 2D transition metal carbides and nitrides. Owning to their attractive properties, such as redox-active surfaces, metallic conductivity, and hydrophilicity, MXenes have been intensively studied for applications in electrocatalysis and electrochemical energy storage. Recently, Ti2CTx MXene was claimed to store over 8 wt% hydrogen. Since MXenes are also electrocatalysts for hydrogen production, investigating hydrogen storage while it is produced on the same material electrode is a promising direction. In this study, we investigated the effect of electrochemical hydrogen production and storage in Ti3C2Tx MXene on cell pressure in a sulfuric acidic electrolyte.

High-Yield Synthesis of Colloidal Carbon Rings and Their Applications in Self-Standing Electrodes of Li-O2 Batteries.

The use of carbon materials in porous electrodes has impressive advantages. However, precisely tailoring the multilevel pore structure of carbon electrodes remains an unsolved challenge. Here, we report a highly efficient site-selective growth strategy to synthesize colloidal carbon rings by templating patchy droplets. Carbon rings are used for the direct fabrication of self-standing porous electrodes with hierarchical pores for lithium-oxygen batteries (LOBs). In situ atomic force microscopy reveals that during discharge the discharge products densely nucleate and grow on carbon rings, demonstrating that such rings are a very potential electrode material in LOBs. The hollow carbon ring electrode (HCRE) possesses micrometer-scale channels formed by random packing of rings and nanochannels consisting of ring-shaped hollow cavities connected by nanosized pores in the wall. Both channels contribute to ion transportation and gas diffusion, but the storage of the discharge products mainly lies in micrometer-scale channels, leading to a high discharge capacity of LOBs (20 658 mAh/g). Our work paves a new way to construct hierarchically porous electrodes for application in electrocatalysis and electrochemical energy storage.

Metal–organic framework and carbon hybrid nanostructures: Fabrication strategies and electrocatalytic application for the water splitting and oxygen reduction reaction

Metal–organic framework and carbon hybrid nanostructures: Fabrication strategies and electrocatalytic application for the water splitting and oxygen reduction reaction

Study of CuSb bimetallic flow-through gas diffusion electrodes for efficient electrochemical CO2 reduction to CO

Electrochemical CO2 reduction (eCO2R) to industrially important feedstock has received great attention, but it faces different challenges. Among them, the poor CO2 mass transport due to low intrinsic CO2 solubility significantly limits the rate of reduction reactions, leading to lower catalytic performance; thereby, commercially relevant current densities can’t be achieved. Moreover, the poor activity and selectivity of high-cost monometallic catalysts, including Cu, Zn, Ag, and Au, undermine the efficiency of eCO2R. Flow-through gas diffusion electrodes (FTGDE), a newly developed class of GDEs, can potentially solve the issue of poor CO2 mass transport because they directly feed the CO2 to the catalyst layer. In addition, abundant surface area, porous structure, and improved triple-phase interface make them an excellent candidate for extremely high rate eCO2R. Antimony, a low-cost and abundant metalloid, can be effectively tuned with Cu to produce useful products such as CO, formate, and C2H4 through eCO2R. Herein, a series of porous binary CuSb FTGDEs with different Sb compositions are fabricated for the electrocatalytic reduction of CO2 to CO. The results show that the catalytic performance of CuSb FTGDEs improved with increasing Sb content up to a certain threshold, beyond which it started to decrease. The CuSb FTGDE with 5.4 g of antimony demonstrated higher current density (206.4 mA/cm2) and faradaic efficiency (72.82 %) at relatively lower overpotentials. Compared to gas diffusion configuration, the poor catalytic activity and selectivity achieved by CuSb FTGDE in non-gas diffusion configuration signifies the importance of improved local CO2 concentration and improved triple-phase interface formation in GDE configuration. The several hours stable operation of CuSb FTGDEs during eCO2R demonstrates its potential for efficient electrocatalytic conversion applications.

Optimization Strategies of Covalent Organic Frameworks and Their Derivatives for Electrocatalytic Applications

AbstractCovalent organic frameworks (COFs) are crystalline organic porous polymers that can be precisely integrated by building blocks to achieve pre‐designed composition, components, and functions, making them a powerful platform for the development of molecular devices in the field of electrocatalysis. The precise control of channel/dopant positions and highly ordered network structures of COFs provide an ideal material system for the applications of advanced electrocatalysis. In this paper, the topological structure design and synthesis methods of COFs are reviewed in detail, and their design principles are deeply analyzed. In addition, the applications of COFs and their derivatives in the field of electrocatalysis are systematically summarized and the optimization strategies are proposed. Finally, the application prospects of COFs and their derivatives in electrocatalysis and the challenges that may be encountered in the future are prospected, providing helpful guidance for future research.

Roughness Factors of Electrodeposited Nanostructured Copper Foams

Copper-based electrocatalytic materials play a critical role in various electrocatalytic processes, including the electroreduction of carbon dioxide and nitrate. Three-dimensional nanostructured electrodes are particularly advantageous for electrocatalytic applications due to their large surface area, which facilitates charge transfer and mass transport. However, the real surface area (RSA) of electrocatalysts is a crucial parameter that is often overlooked in experimental studies of high-surface-area copper electrodes. In this study, we investigate the roughness factors of electrodeposited copper foams with varying thicknesses and morphologies, obtained using the hydrogen bubble dynamic template technique. Underpotential deposition (UPD) of metal adatoms is one of the most reliable methods for estimating the RSA of highly dispersed catalysts. We aim to illustrate the applicability of UPD of lead for the determination of the RSA of copper deposits with hierarchical porosity. To find the appropriate experimental conditions that allow for efficient minimization of the limitations related to the slow diffusion of lead ions in the pores of the material and background currents of the reduction of traces of oxygen, we explore the effect of lead ion concentration, stirring rate, scan rate, monolayer deposition time and solution pH on the accuracy of RSA estimates. Under the optimized measurement conditions, Pb UPD allowed to estimate roughness factors as high as 400 for 100 µm thick foams, which translates into a specific surface area of ~6 m2·g−1. The proposed measurement protocol may be further applied to estimate the RSA of copper deposits with similar or higher roughness.

Atomically dispersed high-loading Pt-Fe/C metal-atom foam catalyst for oxygen reduction in fuel cells

Designing efficient and stable single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) is essential to promote fuel cell commercialization. In this study, the Bayesian Regularization Neural Network (BRNN) has been used to determine the carbothermal shock (CTS) conditions for preparing high-loading Pt-Fe/C SACs. The BRNN model effectively identified a low reaction temperature of 283 °C for achieving high-loading (15 wt %) Pt-Fe/C SACs. Based on this model, we successfully synthesized Pt-Fe/C SACs with a metal mass content of 11.31 wt % using the CTS method. These ultrahigh content metal Pt-Fe/C SACs consisted of dispersed single atoms and foam-like atomic constructions, namely Pt-Fe/C atom foam catalysts (AFCs), rendered them promising candidates for electrocatalysis applications. The Pt-Fe/C AFCs exhibited good catalytic activity and durability toward ORR in alkaline conditions. The Pt-Fe/C AFCs were employed in a direct borohydride fuel cell (DBFC) as cathode catalyst, which resulted in a maximum power density of 214 mW cm−2 at 60 °C and demonstrated stable discharge for 40 h at room temperature. The electrocatalytic performance of the Pt-Fe/C AFCs surpassed that of low-loading Pt-Fe/C SACs and commercial Pt/C catalysts. The rapid ramp-up rate and the rapid cooling rate of the CTS process enabled the incorporation of high-loading Pt and Fe metal atoms into the graphitized carbon layer, resulting in an increased number of active sites of the Pt-Fe/C AFCs. This work provides an effective strategy for manufacturing efficient and stable SACs for practical applications in fuel cells.

Sterically attenuated electronic communication in cobalt complexes of meridional isoquinoline-derived ligands for applications in electrocatalysis.

The ability to synthetically tune the ligand frameworks of redox-active molecules is of critical importance to the economy of solar fuels because manipulating their redox properties can afford control over the operating potentials of sustained electrocatalytic or photoelectrocatalytic processes. The electronic and steric properties of 2,2':6',2″-terpyridine (Terpy) ligand frameworks can be tuned by functional group substitution on ligand backbones, and these correlate strongly to their Hammett parameters. The synthesis of a new series of tridentate meridional ligands of 2,4,6-trisubstituted pyridines that engineers the ability to finely tune the redox potentials of cobalt complexes to more positive potentials than that of their Terpy analogs is achieved by aryl-functionalizing at the four-position and by including isoquinoline at the two- and six-positions of pyridine (Aryl-DiQ). Their cobalt complex syntheses, their electronic properties, and their catalytic activity for carbon dioxide (CO2) reduction are reported and compared to their Terpy analogs. The cobalt derivatives generally experience a positive shift in their redox features relative to the Terpy-based analogs, covering a complementary potential range. Although those evaluated fail to produce any quantifiable products for the reduction of CO2 and suffer from long-term instability, these results suggest possible alternate strategies for stabilizing these compounds during catalysis. We speculate that lower equilibrium association constants to the cobalt center are intrinsic to these ligands, which originate from a steric interaction between protons on the pyridine and isoquinoline moieties. Nevertheless, the new Aryl-DiQ ligand framework has been engineered to selectively tune homoleptic cobalt complexes' redox potentials.

Optimizing Co2+ concentration on high-index Co3O4 facets enhances the catalytic performance in NaBH4 hydrolysis

Hydrogen is a viable alternative to fossil fuels due to its clean-burning properties and high energy density. However, a key challenge lies in the environmentally friendly production and storage of H2. NaBH4 could provide a solution by efficiently storing and releasing H2 through hydrolysis. Current catalysts for NaBH4 hydrolysis often contain cobalt (Co) and precious metals, raising concerns about their environmental impact and cost. To address this, this work proposes the development of efficient Co-only catalysts. Specifically, we explore the role of different crystal facets, specifically (311) and (220), in Co3O4 nanoparticles, demonstrating that an elevated CoO concentration in the (220) facet results in better catalysis for NaBH4 hydrolysis compared to traditional Co/precious metal composites. This improved catalyst shows promise for sustained use and minimal loss of catalytic activity, making it a potential solution for clean H2 production. Additionally, the findings may have broader applications in electrocatalysis and photocatalysis.

A Comprehensive Review on Electrocatalytic Applications of 2D Metallenes.

This review introduces metallenes, a cutting-edge form of atomically thin two-dimensional (2D) metals, gaining attention in energy and catalysis. Their unique physicochemical and electronic properties make them promising for applications like catalysis. Metallenes stand out due to their abundance of under-coordinated metal atoms, enhancing the catalytic potential by improving atomic utilization and intrinsic activity. This review explores the utility of 2D metals as electrocatalysts in sustainable energy conversion, focusing on the Oxygen Evolution Reaction, Oxygen Reduction Reaction, Fuel Oxidation Reaction, and Carbon Dioxide Reduction Reaction. Aimed at researchers in nanomaterials and energy, the review is a comprehensive resource for unlocking the potential of 2D metals in creating a sustainable energy landscape.