High Electrochemical Active Surface Area Research Articles

Partial Selenization Strategy for Fabrication of Ni0.85Se@NiCr-LDH Heterostructure as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

NiCr-LDH and its partial selenization as Ni0.85Se@NiCr-LDH heterostructure is established here as an alkaline water electrolyzer for achieving enhanced overall water splitting efficiency. The hydrothermally synthesized optimized batch of Ni0.85Se@NiCr-LDH is thoroughly characterized to elucidate its structure, morphology, and composition. Compared to pristine NiCr-LDH, the batch of Ni0.85Se@NiCr-LDH exhibits exceptional alkaline OER and HER activity with low overpotentials of 258 and 85 mV at 10 mA cm-2, respectively. Besides, Ni0.85Se@NiCr-LDH also exhibits excellent acidic HER with an overpotential of only 61 mV at 10 mA cm-2, indicating that Ni0.85Se@NiCr-LDH can operate effectively across a wide pH range. The excellent electrochemical stability of Ni0.85Se@NiCr-LDH for 24 h operation is attributed to the formation of a thin layer of SeOx during OER operation. The role of selenization and the effect of Cr in the LDH lattice toward enhanced electrocatalytic water splitting is discussed. The outstanding OER and HER performances of Ni0.85Se@NiCr-LDH are attributed to the higher electrochemical active surface area, favorable conditions for adsorption of HER/OER intermediates, low charge transfer resistance, and improved conductivity. The practical application ofNi0.85Se@NiCr-LDHas a bifunctionalelectrocatalyst for overall water splitting is reflected from the low cell voltage of 1.548 V at 10 mA cm-2.

Advanced (Cu,Co)Se2 Nanocubes and Ti‐MXene Based Screen Printed Electrodes for High Performance Flexible Microsupercapacitors

AbstractNowadays, the demand for portable micro‐energy storage devices with high energy density and scalable printing with cost‐effective fabrication for microsupercapacitors (MSC) are essential. Furthermore, the urgent need for this high‐performance MSC to meet all industrial sector requirements are very challenging. Herein, the screen printable MSC with high energy density is demonstrated by using copper hexacyanocobaltate (CuHCCo) derived (Cu,Co)Se2 nanocubes as the positive electrode and Ti‐MXene (Ti3C2Tx) as the negative electrode. The prepared battery type (Cu,Co)Se2 nanocubes greatly enhance the high electrochemical activity and active surface area. As a result, it delivers a high specific capacity of 602 C g−1 at the current density of 1 A g−1. The fabricated screen printable asymmetric MSC has enhanced ion‐to‐electron transfer in printable microelectrodes with numerous electrochemical active sites and delivered the high areal capacitance of 58 mA cm−2 at the current density of 1 mA cm−2 with a wide potential window. The device gives a high energy density of 8.06 µWh cm−2 and a high power density of 5 mW cm−2. These results demonstrate the new strategies of fabricating electrode materials in screen printable asymmetric MSC and show promising in microscale energy storage devices in the miniaturized devices with sustainable self‐powered compatibility.

Development of an efficient bifunctional electrocatalyst based on Co/CoSe2 nanoparticles embedded in N, Se co-doped carbon for AEMFC and rechargeable Zn-air battery

We suggest a hollow-structured N, Se dual-doped carbon framework embedded with Co/CoSe2 nanoparticles (Co/CoSe2@NSeC) as highly efficient bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The prepared electrocatalyst exhibits high electrochemical active surface area attributed to its unique hollow/porous structure and defective heteroatom doping sites. Furthermore, the strongly coupled heterojunction between Co and CoSe2 species not only provides abundant and highly active sites but also generates built-in electric field, thereby promoting electron transfer during the electrocatalytic reaction. Based on the above considerations, the prepared catalyst shows excellent bifunctional electrocatalytic performance. Leveraging the excellent ORR activity of Co/CoSe2@NSeC, alkaline exchange membrane fuel cells (AEMFC) with the Co/CoSe2@NSeC as air cathode exhibits high power density of 171.23 mW cm2. Furthermore, the rechargeable Zn-air battery employing the Co/CoSe2@NSeC shows high specific capacity (729.4 mAh gZn−1), peak power density (192.88 mW cm2), and sustained stability over 300 cycles.

Dual modification of cobalt silicate nanobelts by Co3O4 nanoparticles and phosphorization boosting oxygen evolution reaction properties

Oxygen evolution reaction (OER) process is the “bottleneck” of water splitting, and the low-cost and high-efficient OER catalysts are of great importance and attractive but they are still challenging. Herein, a dual modification strategy is developed to tune and enrich the structure of cobalt silicate (Co2SiO4) showing boosted OER properties. Cobalt oxide (Co3O4) decorated Co2SiO4 nanobelts, denoted as CS, is firstly prepared using a Co-based precursor by a facile hydrothermal reaction. Then, cobalt phosphide (CoP) nanoparticles are in-situ grown on CS (denoted as CS-P) by the phosphorization process, which provide many active sites and boost the surface reactivity. The experimental results and density function theory (DFT) calculations both reveal that the CoP on CS can improve the conductivity and ensure fast kinetics, thus leading to boost the OER properties of Co2SiO4. When the phosphorization temperature is at 400 °C (CS-P400), it gains the lowest overpotential of 297 mV, which is much lower than CS (340 mV) and Co2SiO4 (409 mV) at 10 mA·cm−2, and even superior to the state-of-the-art transition metal silicates. CS-P400 also achieves high electrochemical active surface area (ECSA) and small Tafel slope owing to its porous structures with large specific surface area and nanosheet-like structures which are good for exposing many active sites and favorable to the fast kinetics. This work not only provides a dual modification route to boost catalytic activity of Co2SiO4 (CS-P400), but also sheds light on a new avenue for developing highly dispersed CoP on silicates to boost OER performances.

Preparation of porous (Mo2/3Y1/3)2AlC and its hydrogen evolution reaction performance

Porous (Mo2/3Y1/3)2AlC MAX phase ceramic was prepared by reaction sintering method using Mo, Y, Al, and graphite powder as raw materials. The influence of changes in Al content on the purity of the obtained samples was investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Archimedes method, and bubble point method. The conditions for obtaining a pure phase were identified, and the transformation path of the phase during sintering and the mechanism of pore formation were provided. The linear sweep voltammetry (LSV) cure and cyclic voltammetry (CV) cure of MAX were tested using an electrochemical workstation. It can be calculated that MAX exhibits good hydrogen evolution reaction (HER) performance under alkaline conditions due to its high electrochemical active surface area (ECSA) of 373.2 and small Tafel slope of 41.7 ​mV·dec−1.

MnCo2O4 Spinel & Carbon Black coated Nickel Foam Electrode. A Bifunctional Water-Splitting Catalyst?

Hydrogen has the potential to revolutionise how we produce and consume energy. We can meet energy demands without compromising the environment by using renewable sources such as wind, solar and wave power producing low-cost electricity to split the water molecule into its constituent parts. We could then convert Hydrogen back to electricity using a fuel cell, as illustrated in Figure 1. The by-product in this entire process is water, giving a clean technology with no toxic or greenhouses gases. Currently the best performing electrocatalytic materials for water splitting are noble metal based, namely platinum for the hydrogen evolution reaction (HER) and Ruthenium for the oxygen evolution reaction (OER). The use of these materials is unsustainable and makes fuel cells too expensive for commercial applications. We must engineer sustainable, cost-effective alternatives.Nickel foam electrodes display desirable electrocatalytic properties such as a large surface area compared to volume with highly conducting, porous networks, while transition metal dichalcogenides show very good electronic properties with high surface areas and large active sites. In this work we show that it is possible to electrochemically and solvothermally produce CoSex and CoSex composites on a porous nickel foam electrode (NFE). The best performing materials were selected and evaluated via electrochemical impedance spectroscopy. This analysis showed high electrochemical active surface area (ECSA) values and good stability across the selected materials. Scanning electron microscopy (SEM) images reveal that the surfaces of the synthesized materials exhibit distinct morphologies and have been significantly modified. Further electrochemical evaluation of the materials reveals low overpotentials for both hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) thus showing promise as a potential bi-functional electrocatalyst in overall water splitting.References(1) Chaudhari, N. K.; Jin, H.; Kim, B.; Lee, K. Nanostructured Materials on 3D Nickel Foam as Electrocatalysts for Water Splitting. Nanoscale. 2017. https://doi.org/10.1039/c7nr04187j.(2) Minadakis, M. P.; Tagmatarchis, N. Exfoliated Transition Metal Dichalcogenide-Based Electrocatalysts for Oxygen Evolution Reaction. Advanced Sustainable Systems. 2023. https://doi.org/10.1002/adsu.202300193.(3) Sukanya, R.; da Silva Alves, D. C.; Breslin, C. B. Review—Recent Developments in the Applications of 2D Transition Metal Dichalcogenides as Electrocatalysts in the Generation of Hydrogen for Renewable Energy Conversion. J Electrochem Soc 2022, 169 (6). https://doi.org/10.1149/1945-7111/ac7172. Figure 1

Platinum-Ruthenium Bimetallic Nanoparticle Catalysts Synthesized Via Direct Joule Heating for Methanol Fuel Cells.

Platinum-Ruthenium (PtRu) bimetallic nanoparticles are promising catalysts for methanol oxidation reaction (MOR) required by direct methanol fuel cells. However, existing catalyst synthesis methods have difficulty controlling their composition and structures. Here, a direct Joule heating method to yield highly active and stable PtRu catalysts for MOR is shown. The optimized Joule heating condition at 1000°C over 50 microseconds produces uniform PtRu nanoparticles (6.32wt.% Pt and 2.97 wt% Ru) with an average size of 2.0 ± 0.5 nanometers supported on carbon black substrates. They have a large electrochemically active surface area (ECSA) of 239 m2 g-1 and a high ECSA normalized specific activity of 0.295mA cm-2. They demonstrate a peak mass activity of 705.9mA mgPt -1 for MOR, 2.8 times that of commercial 20 wt.% platinum/carbon catalysts, and much superior to PtRu catalysts obtained by standard hydrothermal synthesis. Theoretical calculation results indicate that the superior catalytic activity can be attributed to modified Pt sites in PtRu nanoparticles, enabling strong methanol adsorption and weak carbon monoxide binding. Further, the PtRu catalyst demonstrates excellent stability in two-electrode methanol fuel cell tests with 85.3% current density retention and minimum Pt surface oxidation after 24 h.

Constructing novel Sn-Mo bimetallic sulfide heterostructures for enhanced catalytic performance towards the hydrogen evolution reaction

Understanding the design principles of efficient electrocatalysts using the structure–activity relationship is crucial for the advancement of energy-related applications, and specifically the hydrogen evolution reaction (HER). Non-precious electrocatalysts with low overpotentials are essential for driving the HER and achieving high energy efficiency. In this study, we synthesized and thoroughly investigated various heterostructures combining Mo and Sn sulfides, ranging from complete phase-separated hybrids to homogeneous mixtures: SnS@MoS2 core–shell structures, SnS/MoS2 with edge-rich Mo and (SnxMo1-x)S with uniformly distributed Sn-Mo. Our findings reveal that the SnS@MoS2 structure exhibited relatively high intrinsic activity characterized by a high electrochemical active surface area and rapid charge transfer kinetics, thereby enhancing the HER catalytic performance. The presence of fluffy MoS2 layers provided an abundance of optimized sites for HER, potentially due to strain and defects such as S vacancies, known as active catalytic sites. The optimal structure facilitated efficient charge transfer from the core to the shell, improving conductivity and catalytic activity. Our research highlights the advantages of a core–shell hybrid structure, offering guiding principles for the development of an optimal SnS@MoS2 catalyst.

Unravelling the efficacy of pencil graphite anode decorated with PdCu@γ-Fe2O3 nanoparticles in the electro-oxidation of amoxicillin: Insights into kinetics, oxidative pathways and toxicity evaluation

Indiscriminate use of antibiotics has resulted in the occurrence of antibiotic residues in sediments, water bodies and industrial sewage, causing ill effects on aquatic organisms and humans. Electrochemical oxidation process via in-situ generation of strong oxidant •OH is the promising method for the removal of pollutants. In this work, PdCu/γ-Fe2O3 NPs electrodeposited pencil graphite electrode (PdCu/γ-Fe2O3@PGE) has been projected as a cost-effective anode for electro-oxidation of amoxicillin (AMX), while bare PGE was used as a cathode to generate H2O2. The electrochemical measurements showed that PdCu/γ-Fe2O3 @PGE exhibited lower ΔEp (0.191 V), high electrochemical active surface area (ECSA) (0.4620 cm2), higher oxygen evolution potential (OEP) (1.72 V), and lower charge transfer resistance of 9.747 Ω/ cm2 which was ideal for electro-oxidation of AMX. Under the optimum reaction conditions (I = 0.2 mA, pH = 4), the % AMX removal reached 90.5 % after 50 min of electro-oxidation in 0.5 M NaCl. •OH, H2O2, and HOCl were found to be the in-situ generated oxidants. The AMX solution after electro-oxidation did not exhibit antibacterial activity. The toxicity of the formed intermediates were evaluated using Toxicity Estimation Software Tool (T.E.S.T) and found to be less toxic. The electrical energy consumption was estimated to be 0.786 kWhm−3.Thus, modified PGE finds application in the remediation of effluents containing amoxicillin.

Greenly Synthesized CoPBA@PANI as a Proficient Electrocatalyst for Oxygen Evolution Reaction and Its Green Sustainability Assessments.

Water electrolysis is a key factor to generate mobile and sustainable energy sources for H2 production. Cobalt-based Prussian Blue analogues encompassed with polymer support electrocatalysts CoPBAX@PANI (CoPBA@PANI-100, CoPBA@PANI-200, and CoPBA@PANI-300) have been synthesized and characterized. The well-designed CoPBA@PANI-200/GC shows a low overpotential (η10) of 301 mV with a small Tafel slope (56 mV dec-1), comapred to that of IrO2 (348 mV ; 98 mV dec-1) for OER. The conductivity with stability of CoPBAX@PANI have been increased due to the synergistic effect of CoPBA with PANI. PANI provides additional active sites and shows strong binding with Co ions, and the even distribution of CoPBA overcomes the sluggish kinetics. The turnover frequency (TOF) of CoPBA@PANI-200/GC (0.0212, s-1) was ∼15 times higher than IrO2 (0.0014 s-1) at 1.60 V. Furthermore, CoPBA@PANI-200/NF delivers low overpotential of 274 mV@10 mA cm-2 and exhibits a durability of >250 h with a potential loss of 4.2%. Benefiting from strong electronic interaction between polymer support and evenly distributed CoPBA, CoPBAx@PANI shows higher electrochemical active surface area (ECSA) of 53.08 mF cm-2. The solar-based water electrolysis confirmed the practical use of CoPBA@PANI-200/NF (1.57 V) for eco-benign industrial H2 production. The CoPBA@PANI-200 shows exceptional OER performances as well as favorable kinetics to resolve the sluggish water oxidation. Hence, the cost-effective CoPBA@PANI performances opens a prospective way to boost the efficiency of other cobalt-derived catalysts in renewable energy devices.

Defect-rich cypress-leaf-like Cu2+1O@NiF for high-performance non-invasive glucose detection with low detection limit

Non-invasive detection of body fluid glucose concentration is of great significance in the diagnosis and treatment of diabetes, which poses a new challenge to the reduction of the detection limit of glucose sensors. In this work, a novel non-enzymatic glucose sensor (defect-rich cypress-leaf-like Cu2+1O@NiF) was proposed by rapid electrodeposition of cypress-leaf-like Cu2+1O on the surface of nickel foam (NiF) substrate. Due to the high electrochemical active surface area and abundant defects of cypress-leaf-like Cu2+1O providing more catalytic active sites, the prepared non-enzymatic sensor has an ultra-low detection limit (0.9 nM), high sensitivity (88,419.4 μA∙mM−1∙cm−2 (1 nM-0.5 μM) and 2095.5 μA∙mM−1∙cm−2 (1 μM-4.33 mM)) and wide linear range (1 nM-4.33 mM) with good selectivity, reproducibility and stability. Furthermore, the obtained sensors exhibited high detection stability, accuracy and recovery for glucose detection of human body fluid samples, which means that the defect-rich cypress-leaf-like Cu2+1O@NiF electrode is an ideal candidate for non-invasive glucose sensors.

Engineering 1T-MoS2 core-shells unified with nitrogen-rich amorphous carbon nanotube for ratiometric low-level detection of nitroquinoline

Nitroquinolines are an important toxic element in ecosystems and have great significance for monitoring the environmental system with appropriate tools for safety assessments. In this work, we developed a sensitive method for accurate and low-level detection of 5-nitroquinoline (5-NQ) using 1T-molybdenum disulfide core shells unified with nitrogen-rich amorphous carbon nanotube (1T-MoS2/NCNT). The 1T-MoS2/NCNT core-shells composite is prepared using a hydrothermal method to fabricate a ratiometric low-level detection of a 5-NQ sensor. The screen-printed carbon electrode (SPCE) modified with 1T-MoS2/NCNT reveals superior electrochemical performance for the detection of 5-NQ with a wide dual linear range of 0.03–258.58 µM and 274.91–604.25 µM, low-level detection limit (LOD) of 0.0089 µM, and a higher sensitivity of 1.83 µA µM−1 cm−2 due to its higher electrochemical active surface area, superior conductivity, and excellent stability. The π-delocalized electrons in 5-NQ facilitate the rapid electron transfer at the electrode-electrolyte interface, allowing easy conjugation with 1T-MoS2/NCNT. The operational stability of the sensor retains 98.7 % after 40 consecutive cycles. In addition, the achieved recovery rates are 96.80–99.76 % and 97.93–99.75 % for 5-NQ detection in various soils and water samples, signifying its feasibility for real-time industrial waste monitoring.

Effect of hydrothermal reaction temperature on MoO3 nanostructure properties for enhanced electrochemical performance as an electrode material in supercapacitors

This study aims to enhance electrochemical energy storage in supercapacitors by optimizing the synthesis temperature of MoO3 nanostructures using a hydrothermal technique. MoO3 nanostructures were synthesized using a hydrothermal technique, with reaction temperatures ranging from 140 to 230 °C for 24 h. The materials were analyzed using various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, and ultraviolet–visible (UV–Vis) spectroscopy. The findings indicate that at 200 °C, a pure hexagonal phase of MoO3 was obtained, while different temperatures resulted in a combination of orthorhombic and hexagonal phases. The SEM analysis demonstrated that the morphology of the MoO3 nanostructures varied depending on the synthesis temperature. These variations encompass the particles, spherical planar structures, and nanorods. The prepared samples were subjected to electrochemical analysis to explore their electrochemical properties, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge (GCD). The electrochemical performances of the prepared samples varied depending on the temperature at which the MoO3 samples were prepared, resulting in different morphologies. The sample prepared at 220 °C exhibited the highest specific capacitance (CS) of 330 F/g, a minimal charge-transfer resistance (RCT) of 1800 Ω, an energy density of 16.50 Wh/kg, and a power density of 150 W/kg with symmetric and asymmetric device CS values of 125 and 115 F/g, respectively, compared to the other prepared samples. The observed outcomes can be attributed to the diverse morphology of MoO3 nanostructures and the high electrochemical active surface area (ECSA) of 7.43 × 10−5 F/cm2 that were synthesized at different hydrothermal temperatures. This diversity in morphology and ECSA leads to the presence of active surface area sites, thereby enhancing electrochemical activity. These findings highlight the effect of synthesis temperature on the morphology, crystal structure, and electrochemical performance of MoO3 nanostructures for supercapacitor applications.

Achieving Exceptional Volumetric Desalination Capacity Using Compact MoS2 Nanolaminates.

Capacitive deionization (CDI) has emerged as a promising technology for freshwater recovery from low-salinity brackish water. It is still inapplicable in specific scenarios (e.g., households, islands, or offshore platforms) due to too low volumetric adsorption capacities. In this study, a high-density semi-metallic molybdenum disulfide (1T'-MoS2) electrode with compact architecture obtained by restacking of exfoliated nanosheets, which achieve high capacitance up to ≈277.5Fcm-3 under an ultrahigh scan rate of 1000mVs-1 with a lower charge-transfer resistance and nearly tenfold higher electrochemical active surface area than the 2H-MoS2 electrode, is reported. Furthermore, 1T'-MoS2 electrode demonstrates exceptional volumetric desalination capacity of 65.1mgNaClcm-3 in CDI experiments. Ex situ X-ray diffraction (XRD) reveal that the cation storage mechanism with the dynamic expansion of 1T'-MoS2 interlayer to accommodate cations such as Na+, K+, Ca2+, and Mg2+, which in turn enhances the capacity. Theoretical analysis unveils that 1T' phase is thermodynamically preferable over 2H phase, the ion hydration and channel confinement also play critical role in enhancing ion adsorption. Overall, this work provides a new method to design compact 2D-layered nanolaminates with high-volumetric performance for CDI desalination.

Enhancing the physicochemical properties of nickel cobaltite catalyst for oxygen evolution reaction in anion exchange membrane water electrolyzers

Hierarchical hollow urchin-like nickel cobaltite (NiCo2O4) was synthesized using a two-step hydrothermal method. The effects of metal composition and surfactant addition on the morphology, structure, and electrochemical performance toward oxygen evolution reaction (OER) were investigated. The addition of cetyltrimethylammonium bromide (CTAB) reduced particle aggregation, resulting in a higher electrochemical active surface area and electrical conductivity. Lowering the Ni content from 1.0 to 0.25 did not alter the morphology and structure of the product to any extent. However, the crystallite size slightly increased. Among the spinels with different Ni and Co compositions, NiCo2O4 exhibited a superior OER electrocatalytic activity, achieving a 380 mV overpotential at 10 mA/cm2 current density. It also delivered a good performance in an anion exchange membrane water electrolyzer (AEMWE) using 1 M NaOH at 60 °C, reaching a current density of about 420 mA/cm2 at a cell voltage of 1.95 V.

Controllable boosting activity on Co4N by Fe substitution for oxygen evolution reaction and efficient 5-hydroxymethylfurfural oxidation

The design of transition metal nitrides with excellent oxygen evolution reaction and 5-hydroxymethylfurfural oxidation reaction (HMFOR) is of great significance to achieve the goal of "carbon peaking and carbon neutrality". Herein, Fe-doped bimetallic nitride FexCo1-x)4N was prepared by a simple electron regulation strategy. The introduction of Fe changes the electronic structure of Co and optimizes the adsorption energies of *OH, reduces the potential barrier for the generation of *OOH as a potential-determining step and thus increases the intrinsic OER activity of Co4N. In addition, Fe substitution of some of the Co atoms gives (FexCo1-x)4N a higher electrochemical active surface area, which accelerates the electron transfer efficiency and improves the electrical conductivity. The overpotential for (FexCo1-x)4N-0.9 to reach a current density of 10 mA cm−2 in 1 M KOH is only 271 mV. When in 1 M KOH + 50 mM HMF condition, (FexCo1-x)4N-0.9 requires only 1.37 V to reach a current density of 10 mA cm−2. This work provides practical guidance for developing bifunctional transition metal electrocatalysts with excellent OER and HMFOR activity.

Electrocatalytic sensing of propyl gallate in real-time food samples using a synergistic Sm-MOF@GCN composite modified glassy carbon electrode

A novel electrochemical sensor has been developed using the sonochemically synthesized samarium metal–organic framework (Sm-MOF) and the graphitic carbon nitride (GCN) composite for the selective determination of propyl gallate (PG). The as-synthesized Sm-MOF@GCN composite was characterized by XRD, XPS, and FESEM. The morphological studies of the prepared Sm-MOF@GCN composite revealed the bar-shaped Sm-MOF and porous sheet-like morphology of GCN. The combined effect of the Sm-MOF and GCN enhance the current density response and lowers the oxidation potential, which was beneficial for the electrochemical sensing of PG. Moreover, the high electrochemical active surface area (EASA) (0.0649 cm2) and the rate constant value (Ko) of 1.44x10-5 cm s−1 confirm the faster electron transfer kinetics at the interface of Sm-MOF@GCN composite. However, the developed Sm-MOF@GCN composite possesses linear range from 0.02 to 60 µM with a nanomolar detection level (2.05 nM), high sensitivity (0.1914 μA μM−1 cm−2), excellent reproducibility, repeatability, and stability for up to 30 days towards the PG detection. Finally, the Sm-MOF@GCN composite-modified electrocatalyst was utilized for the quantification of PG in foodstuffs such as instant noodles, cookies, cakes, and oils. The result of the study, the Sm-MOF@GCN composite displayed good recovery results, making it a promising candidate for detecting PG in real-world samples in view of its binder-free approach and facile fabrication process.

Preparation of highly active and durable electrodes for alkaline water electrolysis by anodizing of commercial FeNi and FeNiCo alloys

Anodizing is gaining popularity as a binder-free fabrication route for obtaining catalyst materials directly on the current collector without using noble metals, binders, or conductive carbon additives. Here, we fabricate promising highly active electrodes for alkaline water electrolysis by anodizing commercial FeNi and FeNiCo alloys (%wt. Fe range between 22 and 63) in an ethylene glycol-based fluoride electrolyte. Anodizing forms metal fluoride coatings, which are converted to OER active compounds (γ-NiOOH:Fe) during potential cycling in an alkaline aqueous solution (1 mol L−1 (M) KOH at 293 K) as a result of leaching of fluoride ions. The morphology, thickness, and number of active sites are influenced by the amount of Fe in the alloy, and the electrode with the highest electrochemical active surface area (Kovar alloy with a 54 %wt. Fe) shows the largest OER activity enhancement by anodizing. The performance evaluation in practical conditions (7 mol L−1 KOH at 343 K) demonstrated a highly active performance with an OER potential as low as 1.52 V at a current density of 600 mA cm−2 even for electrodes obtained in alloys with a low amount of Fe (78-Permalloy with a 22 %wt. Fe), demonstrating that anodizing is an effective way to develop highly active OER electrodes from commercially available alloys. On the other hand, anodizing is a good fluoridation route for transition metals with good results in the formation of F-enriched precursors that efficiently promote active phase formation during the catalytic process, offering the possibility of obtaining catalysts directly on the current collector in a one-step process, easily implemented in industrial applications.

Green and sustainable use of macadamia nuts as support material in Pt-based direct methanol fuel cells

The successful commercialization of direct methanol fuel cells (DMFCs) is hindered by inadequate methanol oxidation activity and anode catalyst longevity. Efficient and cost-effective electrode materials are imperative in the widespread use of DMFCs. While Platinum (Pt) remains the primary component of anodic methanol oxidation reaction (MOR) electrocatalysts, its utilization alone in DMFC systems is limited due to carbon monoxide (CO) poisoning, instability, methanol crossover, and high cost. These limitations impede the economic feasibility of Pt as an electrocatalyst. Herein, we present the use of powdered activated carbon (PAC) and granular activated carbon (GAC), both sourced from macadamia nut shells (MNS), a type of biomass. These bio-based carbon materials are integrated into hybrid supports with reduced graphene oxide (rGO), aiming to enhance the performance and reduce the production cost of the Pt electrocatalyst. Electrochemical and physicochemical characterizations of the synthesized catalysts, including Pt-rGO/PAC-1:1, Pt-rGO/PAC-1:2, Pt-rGO/GAC-1:1, and Pt-rGO/GAC-1:2, were conducted. X-ray diffraction analysis revealed crystallite sizes ranging from 1.18 nm to 1.68 nm. High-resolution transmission electron microscopy (HRTEM) images with average particle sizes ranging from 1.91 nm to 2.72 nm demonstrated spherical dispersion of Pt nanoparticles with some agglomeration across all catalysts. The electrochemical active surface area (ECSA) was determined, with Pt-rGO/GAC-1:1 exhibiting the highest ECSA of 73.53 m2 g−1. Despite its high ECSA, Pt-rGO/GAC-1:1 displayed the lowest methanol oxidation reaction (MOR) current density, indicating active sites with poor catalytic efficiency. Pt-rGO/PAC-1:1 and Pt-rGO/PAC-1:2 exhibited the highest MOR current densities of 0.77 mA*cm−2 and 0.74 mA*cm−2, respectively. Moreover, Pt-rGO/PAC-1:2 and Pt-rGO/PAC-1:1 demonstrated superior electrocatalytic mass (specific) activities of 7.55 mA/mg (0.025 mA*cm−2) and 7.25 mA/mg (0.021 mA*cm−2), respectively. Chronoamperometry tests revealed Pt-rGO/PAC-1:2 and Pt-rGO/PAC-1:1 as the most stable catalysts. Additionally, they exhibited the lowest charge transfer resistances and highest MOR current densities after durability tests, highlighting their potential for DMFC applications. The synthesized Pt supported on PACs hybrids demonstrated remarkable catalytic performance, stability, and CO tolerance, highlighting their potential for enhancing DMFC efficiency.

Insights into synergetic modulation of nickel sites over graphene by introducing tungsten and light for efficient methanol electrooxidation

Cut-lost, highly active and stable (photo-)electrocatalysts are earnestly expected to overcome high energy obstacles in methanol oxidation reaction (MOR). A hybrid of NiW/graphene (NiW/G) is prepared by a simple self-designed electrosynthesis method. During the process of electrosynthesis, exfoliation of bulky graphite into graphene and generation of multivalent NiW bimetal precursor are both achieved. This obtained composite displays superior photoelectrocatalytic performance towards MOR. As for NiW/G-light, its area activity (peak current) and mass activity (peak current) are up to 343.4 mA cm−2 and 5960.7 mA mg−1 respectively, much higher than NiW/G, Ni/G and W/G. Operando electrochemical impedance spectroscopy, in-situ Fourier transform infrared spectroscopy and other ex-situ techniques uncover that the excellent MOR performance for NiW/G-light results from synergetic modulation of nickel sites by introducing tungsten and light, which provides desired adsorption behavior and high electrochemical active surface area. It’s found that introduction of W component promotes the formation of W-O-Ni(Ni3+) species, supporting more strong adsorption sites for methanol. This results in new reaction path between adsorbed methanol and OH* for producing formic acid. With application of light, the photo-generated hole promotes oxidation of residual Ni2+ into Ni3+ species, which provides additional formed NiOOH sites for MOR. It’s concluded introduction of tungsten and light is efficient for greatly enhancing methanol electrooxidation. This work is highly instructive for application of self-designed electrosynthesis method to construct dimetal/graphene composite and photoelectric synergistic catalysis towards MOR.