Performance Of Electrocatalysts Research Articles

Navigating Alkaline Hydrogen Evolution Reaction Descriptors for Electrocatalyst Design

The quest for efficient green hydrogen production through Alkaline Water Electrolysis (AWE) is a critical aspect of the clean energy transition. The hydrogen evolution reaction (HER) in alkaline media is central to this process, with the performance of electrocatalysts being a determining factor for overall efficiency. Theoretical studies using energy-based descriptors are essential for designing high-performance alkaline HER electrocatalysts. This review summarizes various descriptors, including water adsorption energy, water dissociation barrier, and Gibbs free energy changes of hydrogen and hydroxyl adsorption. Examples of how to apply these descriptors to identify the active site of materials and better design high-performance alkaline HER electrocatalysts are provided, highlighting the previously underappreciated role of hydroxyl adsorption-free energy changes. As research progresses, integrating these descriptors with experimental data will be paramount in advancing AWE technology for sustainable hydrogen production.

Surface Reconstruction Regulation of Co3N Through Heterostructure Engineering Toward Efficient Oxygen Evolution Reaction.

Oxygen evolution reaction (OER) electrocatalysts generally experience structural and electronic modifications during electrocatalysis. This phenomenon, referred to as surface reconstruction, results in the formation of catalytically active species that act as real OER sites. Controlling surface reconstruction therefore is vital for enhancing the OER performance of electrocatalysts. In this study, a new approach is introduced of heterostructure engineering to facilitate the surface reconstruction of target catalysts. Using MnCo carbonate hydroxide (MnCo─CH)@Co3N as a demonstration, it is discovered that the surface reconstruction occurs more readily and rapidly on MnCo─CH@Co3N than on Co3N. More interestingly, during the reconstruction process, Mn species migrate to the surface, enabling the in situ formation of highly active Mn-doped CoOOH. Consequently, the MnCo─CH@Co3N catalyst after reconstruction exhibits a low overpotential of 257mV at 10mAcm-2, compared to 379mV of individual Co3N. This work offers fresh perspectives on understanding the enhanced OER performance of heterostructure electrocatalysts and the role of heterostructure in promoting surface reconstruction.

Highly efficient p-p heterojunction Co3S4/NiS2 electrocatalyst for water splitting and electrochemical oxidation of organic molecules

Organic small molecular-assisted water splitting technology is an efficient and promising technology for hydrogen production, which can meet the needs of obtaining hydrogen energy and protecting the environment. Constructing heterojunctions to enhance the interfacial electron transfer and achieve bifunctionality represents a viable strategy for enhancing the performance of electrocatalysts. In this work, the hollow structure Co3S4/NiS2 p-p heterojunction catalyst has been successfully synthesized by one-step hydrothermal method. Only −0.184, 1.64, 1.44 and 1.56 V vs. RHE are required to drive 50 mA cm−2 for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), urea oxidation reaction (UOR), oxygen evolution reaction in lactic acid solution (OER-LA), respectively. For two-electrode electrolytic process, the cell voltages only need 1.72 V, 1.51 V and 1.61 V to drive 50 mA cm−2 in 1 M KOH, 1 M KOH containing 0.5 M urea and 1 M KOH containing 0.5 M lactic acid electrolytes, and it operates continuously at 50 mA cm−2 for 200 h test without significant decay of activity in 1 M KOH containing 0.5 M lactic acid, showing excellent durability. Density functional theory (DFT) calculation reveals that the p-p heterojunction between Co3S4 and NiS2 facilitates the electron redistribution at interfaces, thereby promoting the electron migration. This work presents a strategic approach for fabricating advanced bifunctional electrocatalysts by employing metal sulfides to form heterojunction, thereby achieving enhanced electrocatalytic activities in both hydrogen production and organic molecule decontamination.

Exploring the role of redox-active species on NiS-NiS2 incorporated sulfur-doped graphitic carbon nitride nanohybrid as a bifunctional electrocatalyst for overall water splitting

The advancement of effective and robust catalysts that can replace the precious-metal-based benchmarks for electrocatalytic overall water splitting is a highly fashionable approach to exploring sustainable energy utilization and addressing environmental issues. Herein, we demonstrate a facile single-step fabrication of NiS-NiS2 nanoparticles in situ grown on the layered porous sulfur-doped graphitic carbon nitride nanosheets (NiS-NiS2/SGCN) act as bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium.Further, an increasing the Ni precursor (fixed sulfur source) increases the formation of NiS-NiS2 on the surface of SGCN (labeled as NS-1.0, NS-2.0, and NS-3.0). Structural and morphological studies such as PXRD, XPS, FTIR, HR-TEM, etc., revealed a uniform distribution of NiS/NiS2 on the surface of S-g-C3N4 nanosheets. The OER and HER activity of NiS-NiS2/SGCN nanohybrid were significantly enhanced by increasing the affinity of accessible surface-active edge sites, interfacial contact allows effective modification of electronic structure, high structural porosity, redox-active centers of Ni2+/Ni3+, and rich in sulfur vacancy. In addition, the enhancement of the exposure of the edge sites is improved by their attachment to a sulfur-doped g-C3N4 framework. As a result, in the half-cell experiments, the NiS-NiS2/SGCN (NS-3.0) catalyst exhibited enhanced performance in both OER and HER, requiring an overpotential of 298 mV to reach 50 mA/cm2 for OER and −144 mV to reach 10 mA/cm2 for HER. Furthermore, the constructed electrolyzer using Ni-S 3.0 as the cathode and anode required a cell voltage of 1.66 V to yield 50 mA/cm2 in overall water splitting. This study may inspire the in-situ synthesis of different metal sulfides on SGCN to provide a unique interfacial approach for improving the performance of bifunctional non-precious electrocatalysts.

Constructing core-shell structured Mott–Schottky heterojunction towards remarkable hydrogen production from water/seawater splitting

Green hydrogen production through electrocatalytic water/seawater splitting has recently received significant attention. However, the practical utilization for this technique is still limited due to the poor performance and stability of electrocatalysts. Herein, a heterogeneous core-shell hybrid, containing Ni3S2 nanorod arrays and CoFe layered double hydroxide (LDH) nanosheets, has been fabricated via a developed two-step hydrothermal and electrodeposition method. The build-in electronic field in the as-formed Mott–Schottky barrier endows the efficient electron transfer from CoFe LDH to Ni3S2, subsequently enhancing the reaction kinetics. The as-prepared Ni3S2@CoFe catalyst exhibits exceptional performance for oxygen evolution reaction (OER, η10 = 222 and 237 mV) and hydrogen evolution reaction (HER, η10 = 83 and 109 mV) in 1 M KOH as well as alkaline seawater environments, respectively. Notably, it only requires a cell voltage of 1.51 and 1.55 V to achieve a current density of 10 mA cm2 for overall seawater and water splitting, respectively, outperforming the commercial benchmark Pt/C||RuO2 (1.56 V). This work paves a solid way for construction of Mott–Schottky catalysts for green hydrogen production and its beyond.

Superaerophobic Ni3N/Ni@W2N3 multi-heterointerfacial nanoarrays for efficient alkaline electrocatalytic hydrogen evolution reaction

The hydrogen evolution performances of electrocatalysts are greatly restricted by their unfavorable hydrogen evolution kinetics and the undesirable accumulation of as-evolved gas bubbles on the electrocatalysts surface. Herein, we present the fabrication of self-supporting multi-heterointerfacial nanoarrays electrode toward addressing these challenges simultaneously. A monolith Ni3N/Ni@W2N3 electrode is prepared, which exhibits a multi-heterojunction interface between the different components. The construction of this multi-heterojunction interface allows for the redistribution of the electrons, thus alleviating the strong Ni-H bond and optimizing the hydrogen adsorption free energy toward more efficient HER catalysis. Moreover, by virtue of the distinct nanoarray structure, the Ni3N/Ni@W2N3 nanoarrays exhibit improved hydrophilicity and superaerophobicity compared with Ni/Ni3N, facilitating water contact and enabling more efficient detachment of the as-evolved H2 bubbles from the surface. Benefiting from these attractive features, the Ni3N/Ni@W2N3 nanoarrays deliver an attractive alkaline HER catalytic activity with a low overpotential of 66 mV to achieve a current density of 10 mA cm−2, which is comparable with that of the benchmark Pt/C electrode. Moreover, the electrode exhibits remarkable stability during long-term electrolysis. The simultaneous interface and nanostructure engineering provide a feasible pathway for obtaining high-performance electrodes and beyond for various electrochemical reactions.

Design and Preparation at Scale of Ternary NiFe-M-Ox (M=Co, Mo) Catalysts for OER in Alkaline Media

Due to scarcity of Platinum Group Metals (PGMs) widely used in low temperature water electrolysis as cathodes (Hydrogen Evolution Reaction; HER) and anodes (Oxygen Evolution Reaction; OER) a boosting interest to their substitution to Earth abundant elements is observed. It was successfully demonstrated that elements like iron, nickel, cobalt and other (in their oxide and hydroxide forms) can be effective OER catalysts when operate at high pH ranges from 12 to 14 [1-3].This work is devoted to systematic investigation of influence of third element addition to NiFeOx system on a performance and stability of catalysts in alkaline OER. As a co-catalytic elements Mo and Co were selected, based on our previous experience [4,5]. A systematic study on an effect of NiFe-to-M ratio, concentration of precipitation agent and post-treatment temperature were evaluated in a wide range of parameters. Taking into account that mass loading of PGM-free OER catalysts is substantially higher than iridium/ruthenium once and can be up to several milligrams per cm2 all experiments were designed to be scalable. In a laboratory scale reactor, a fascinating batch size of 25g was achieved, using minimal amount of water-based solvents in order to minimize a waste stream generated. Presentation will discuss characterization of obtained materials by SEM, TEM, XPS, XRD and other methods as well as their performance, stability and durability in alkaline conditions, studying Oxygen Evolution Reaction. Acknowledgements and Statements. The authors acknowledge financial support from H2NEW and ElectroCat consortia. References. [1] X. Lyu, J. Li, J. Yang, A. Serov "Significance of Slight Ambient Temperature Variation on the Electrocatalyst Performance toward Oxygen Evolution Reaction" Journal of Environmental Chemical Engineering (2023).[2] X. lyu, A. Serov “Cutting-edge methods for amplifying the oxygen evolution reaction during seawater electrolysis: a brief synopsis” Ind. Chem. Mater., (2023).[3] X. Lyu, Y. Bai, J. Li, R. Tao, J. Yang, A. Serov "Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis" J. of Environmental Chemical Engineering 11 (2023) 109667.[4] A. Serov,N. I. Andersen, A. J. Roy, I. Matanovic, K. Artyushkova, P. Atanassov “CuCo2O4 ORR/OER Bi-Functional Catalyst: Influence of Synthetic Approach on Performance”, J. of The Electrochem. Soc. 162 (4) (2015) F449-F454.[5] N. I. Andersen, A. Serov, P. Atanassov “Metal Oxides/CNT Nano-Composite Catalysts for Oxygen Reduction/Oxygen Evolution in Alkaline Media”, Appl. Catal. B: Environmental 163 (2015) 623-627.

CoSex and CoSex/Reduced GO Composites as Electrocatalysts for Water Splitting

Hydrogen stands as an attractive energy source, offering a way to meet increasing energy demands without the reliance on fossil fuels and thus harming the environment. Renewable energy sources such as wind, wave and solar power can be used to generate inexpensive electricity, which we can then use to power water electrolysis.1 The generated hydrogen can then be converted back into electricity by using fuel cells, leaving only water as a by-product, rendering this technology clean and devoid of harmful emissions. The electrolysis cell can be operated at normal room temperatures without the need for high pressure rectors. At present, the practical application of hydrogen production using electrochemical water splitting is hindered by electrocatalyst limitations. Currently, the best electrocatalytic materials for water splitting are Platinum-based for the hydrogen evolution reaction (HER) and Ruthenium-based for the oxygen evolution reaction (OER). These materials are expensive and have limited reserves, 2 and therefore cost-effective alternatives must be developed. Transition metal dichalcogenides (TMDs) are of particular interest due to their tuneable structures. 3,4 Herein we have chosen to investigate CoSe2 as a potential electrocatalyst for overall water splitting (OWS). We describe both the electrochemical and solvothermal synthesis of CoSex. The CoSex was then combined with a carbon substrate to create a total of four electrocatalysts. Reduced graphene oxide (rGO) was employed as the carbon substrate and was synthesised via modified Hummer’s method, drop casted on to a GCE and electrochemically reduced to create a rGO modified GCE. The electrodeposited CoSex/rGO composite (ED-CoSex/rGO) was prepared by immersing a rGO modified GCE in an electrodeposition solution and deposited by holding the electrode at a fixed potential for a period of time (Figure 1). The solvothermal/rGO composite ST-CoSex/rGO was prepared by drop casting the solvothermally prepared CoSex ink on top of a rGO modified GCE. While most of the investigation on these electrocatalysts was done using simple glassy carbon electrode (GCE), the best performing material was then screened on a more porous electrode such as Nickel Foam (NF).Materials were characterised using a combination of HR-SEM, XRD, Raman and XPS, while cyclic voltammetry, linear sweep voltammetry and chronoamperometry were employed to examine catalytic activity of the materials. SEM unveiled distinct morphologies, with the electrochemically formed CoSex appearing as flower-like deposits, while sheet-like morphology was seen with the solvothermal synthesis. The solvothermally produced CoSex was more crystalline, as evidenced from XRD. Despite the morphological differences, both CoSex variants exhibited commendable electrochemical attributes.Materials also showed good stability over a period of 18 hours with the ED-CoSex material showing the best performance over 18 hours. Interestingly, all materials showed improved HER performance when subsequently tested after 18 hours via polarisation curves. All materials exhibited high electrochemical active surface areas (ECSA), stability, and favourable low overpotentials for both the hydrogen evolution reaction (HER) and the Oxygen evolution (OER) in alkaline media, however. It is worth noting that while the introduction of rGO significantly lowers the overpotential of electrodeposited and solvothermally synthesised materials, following chronoamperometry, it appears the beneficial effect of the rGO addition is less evident. These results underscore the potential efficacy of CoSex and CoSex composites in facilitating efficient water splitting for hydrogen production, with the potential to rival the performance of platinum-based electrocatalysts. The significance of this research lies in offering sustainable alternatives to platinum in electrolysers, a crucial step toward establishing a more accessible and eco-friendly hydrogen economy.References(1) Jacobson, M. Z.; Delucchi, M. A.; Bazouin, G.; Bauer, Z. A. F.; Heavey, C. C.; Fisher, E.; Morris, S. B.; Piekutowski, D. J. Y.; Vencill, T. A.; Yeskoo, T. W. 100% Clean and Renewable Wind, Water, and Sunlight (WWS) All-Sector Energy Roadmaps for the 50 United States. Energy Environ Sci 2015, 8 (7). https://doi.org/10.1039/c5ee01283j.(2) Anantharaj, S.; Ede, S. R.; Sakthikumar, K.; Karthick, K.; Mishra, S.; Kundu, S. Recent Trends and Perspectives in Electrochemical Water Splitting with an Emphasis on Sulfide, Selenide, and Phosphide Catalysts of Fe, Co, and Ni: A Review. ACS Catalysis. 2016. https://doi.org/10.1021/acscatal.6b02479.(3) 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.(4) 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

Low-Temperature Wastewater Electrolysis for H2 and Clean Water Generation

Water electrolysis represents a sustainable approach to produce green hydrogen (H2); however, the high energy cost (H2O → 2H+ + 2e- + ½O2, ∆H° = 275 kJ/mol H2, E° = −1.18 V) associated with water electrolysis and electricity cost (>$50/MWh) results in a minimum H2 selling price ≈$4/kg H2. Hence, we need to find alternative process to generate H2 to meet the current U.S. Department of Energy's (DOE's) Energy Earthshots of $1/kg H2 in one decade.Wastewater electrolysis represents an alternative approach to generate H2 with renewable sources by electrochemically oxidizing organic molecules to generate H2 (e.g., CH3COOH + 2H2O → 2CO2 + 8e- + 8H+, ∆H° = 53 kJ/mol, E° = −0.02 V,) which has up to 5 times lower energy requirement than water electrolysis. As opposed to water electrolysis that requires clean water streams, wastewater electrolysis uses readily available waste streams that need cleanup anyway to generate H2; hence, integrating a second application in addition to H2 generation.1-3 In this work, we compare the performance of heterogeneous electrocatalysts for the electrocatalytic oxidation (ECO) of organic molecules present in wastewater as well as electrocatalysts for the H2 evolution reaction (HER) at room temperature. ECO electrocatalysts were developed and tested using real wastewaters derived from several sources including the hydrothermal liquefaction (HTL) of food waste. We synthesized the ECO electrocatalysts using both platinum-group metals (PGM) as well as base-group metals (BGM) with equimolar loadings and tested them as a function of half-cell potential. Our results show that both PGM- and BGM-based bimetallics improve the activity and stability compared to the baseline RuO2-based catalysts4-6. We performed a preliminary techno-economic analysis and showed that the levelized costs of using this technology to process the wastewater alone is equivalent to that of traditional wastewater processing. The sale of the produced H2 co-product will decrease the levelized processing cost below that of current wastewater processing. References Andrews, E.; Lopez-Ruiz, J. A.; Egbert, J. D.; Koh, K.; Sanyal, U.; Song, M.; Li, D.; Karkamkar, A. J.; Derewinski, M. A.; Holladay, J.; Gutiérrez, O. Y.; Holladay, J. D., Performance of Base and Noble Metals for Electrocatalytic Hydrogenation of Bio-Oil-Derived Oxygenated Compounds. ACS Sustainable Chemistry & Engineering 2020, 8 (11), 4407-4418.Lopez-Ruiz, J. A.; Qiu, Y.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic valorization into H2 and hydrocarbons of an aqueous stream derived from hydrothermal liquefaction. Journal of Applied Electrochemistry 2021, 51 (1), 107-118.Lopez-Ruiz, J. A.; Andrews, E.; Akhade, S. A.; Lee, M.-S.; Koh, K.; Sanyal, U.; Yuk, S. F.; Karkamkar, A. J.; Derewinski, M. A.; Holladay, J.; Glezakou, V.-A.; Rousseau, R.; Gutiérrez, O. Y.; Holladay, J. D., Understanding the Role of Metal and Molecular Structure on the Electrocatalytic Hydrogenation of Oxygenated Organic Compounds. ACS Catalysis 2019, 9 (11), 9964-9972.Qiu, Y.; Lopez-Ruiz, J. A.; Zhu, G.; Engelhard, M. H.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic decarboxylation of carboxylic acids over RuO2 and Pt nanoparticles. Appl. Catal. B-Environ. 2022, 305, 121060.Lopez-Ruiz, J. A.; Qiu, Y.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic valorization into H2 and hydrocarbons of an aqueous stream derived from hydrothermal liquefaction. J. Appl. Electrochem. 2021, 51 (1), 107-118.Qiu, Y.; Lopez-Ruiz, J. A.; Sanyal, U.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Anodic electrocatalytic conversion of carboxylic acids on thin films of RuO2, IrO2, and Pt. Appl. Catal. B-Environ. 2020, 277, 119277. Figure 1

Key Factors for Electrochemical Carbon Dioxide Reduction at Ni-N-C Catalysts

Electrochemical carbon dioxide reduction reaction (CO2RR) has the potential to adequately contribute to addressing the energy and environmental challenges faced by the humanity today. The surplus of CO2 produced by burning fossil fuels can be transformed into valuable products by CO2RR. An effective use of this approach on a large scale requires active, selective, and stable CO2 reduction electrocatalysts. Additionally, insightful understanding of interfacial behavior such as water wetting and carbonate formation at the electrode is required to enhance the performance and durability of CO2RR electrocatalysts.1 Atomically dispersed Ni-N-C materials have attracted attention due to their superior selectivity for CO generation.2 Their activity and selectivity of CO2RR are influenced by the metal center and local atomic defects in M-N-C catalysts.3 In addition to catalyst structures, electrode composition and structure have also substantial impact on the activity and selectivity of CO2RR. Particularly, ionomer compositions and the electrode fabrication process can alter the hydrophobicity of the electrode and the local pH on the catalyst, resulting in considerable changes in CO2RR activity and selectivity.In this presentation, we will report on the performance of various electrodes fabricated with the Ni-N-C catalyst, using different types of ionomers and measured in a flow cell and zero-gap electrolyzer at > 100 mA/cm2 current densities for CO2RR. We will also introduce an approach that aims at reducing carbonate formation at the CO2RR electrolyzer cathode by the modifications to the electrolyte composition, the CO2 inlet humidity, and the electrochemical cell temperature. Acknowledgement Research presented in this work was supported by the Laboratory Directed Research and Development program of Los Alamos National Laboratory under project number 20230065DR. References (1) Sa, Y. J.; Lee, C. W.; Lee, S. Y.; Na, J.; Lee, U.; Hwang, Y. J. Catalyst–electrolyte interface chemistry for electrochemical CO2 reduction. Chemical Society Reviews 2020, 49 (18), 6632-6665.(2) Wu, J.; Sharifi, T.; Gao, Y.; Zhang, T.; Ajayan, P. M. Emerging Carbon-Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value-Added Chemicals. Advanced Materials 2019, 31 (13), 1804257.(3) Liang, S.; Huang, L.; Gao, Y.; Wang, Q.; Liu, B. Electrochemical Reduction of CO2 to CO over Transition Metal/N-Doped Carbon Catalysts: The Active Sites and Reaction Mechanism. Advanced Science 2021, 8 (24), 2102886.

Towards High-Performance AEM Water Electrolyzers: Transitioning from PGM to Low-PGM and PGM-Free Electrocatalysts

Hydrogen, known for its high gravimetric energy density and low environmental impact, is widely regarded as a promising low-carbon energy carrier. The production of hydrogen via water electrolysis offers a valuable opportunity to efficiently utilize renewable energy resources – both as a storage and transport medium and to produce hydrogen that is a crucial feedstock for multiple industrial and manufacturing applications. Among various water electrolysis technologies, anion exchange membrane water electrolyzers (AEMWEs) are notable for their distinct and advantageous features. Their alkaline operational environment significantly reduces corrosion, allow for the possibility to use catalysts and cell component materials that are earth abundant and cost effective. Moreover, the use of anion exchange membranes (AEMs) as the electrolyte and zero-gap design enhance operational efficiency and hydrogen production rates compared to traditional alkaline electrolyzers. These benefits position AEMWEs as a compelling solution for efficient, cost-effective large-scale hydrogen production.To date, the development of lower-cost AEMWEs has been hindered by several challenges. A critical issue is the activity and durability of catalysts, particularly those that are platinum group metal (PGM)-free. This leads many researchers and electrolyzer manufacturers to lean on PGM catalysts at both the anode and cathode. These catalysts, while effective, significantly increase the cost and complexity of the system, posing a barrier to widespread adoption and commercialization of AEMEL technology in the burgeoning hydrogen economy. PGM-free anodes have been demonstrated for the AEMWE, but there have been fewer PGM-free options for the cathode.This study assessed the performance and durability of various low-PGM and PGM-free electrocatalysts for the oxygen evolution (OER) and hydrogen evolution (HER) reactions. We focused on Lanthanum Strontium Cobalt (LSC), Nickel Ferrite (NiFeOx), and Lead Ruthenate (PbRuOx) for the OER at the anode, and Nickel Molybdenum (NiMo), Nickel Rhenium (NiRe), and a low-PGM PtNi for the HER at the cathode. Furthermore, the performance of the NiMo HER catalyst was enhanced by optimizing the physical properties of both the catalyst powder and the electrodes. These experimental results offer crucial insights into developing PGM-free AEM water electrolyzer systems, marking a progressive step towards their commercial feasibility.

Modeling Diurnal and Annual Ethylene Generation from Solar-Driven Electrochemical CO2 Reduction Devices

Integrated solar fuels devices for CO2 reduction (CO2R) are a promising technology class towards achieving net-negative carbon emissions. Designing integrated CO2R solar fuels devices requires careful co-design of electrochemical and photovoltaic components as well as consideration of the diurnal and seasonal effects of solar irradiance, temperature, and other meteorological factors expected for ‘on-sun’ deployment. Using a photovoltaic-electrochemical (PV-EC) platform, we developed a temperature and potential-dependent diurnal and annual model using experimental CO2R performance of Cu-based electrocatalysts, local meteorological data from the National Solar Radiation Database (NSRD), and modeled performance of commercial c-Si PVs. We simulated diurnal product outputs with and without the effects of ambient temperature to determine gaseous product temperature sensitivity. From these outputs, we observed seasonal variation in gaseous product generation, with up to two-fold increases in ethylene productivity between the Winter and Summer, analyzed the consequences of dynamic cloud coverage, and identified periods where device cooling/heating mechanisms could be implemented to maximize ethylene generation. Finally, we modeled the annual ethylene generation for a scaled 1 MW solar farm at three different locations (Beijing, CN; Sydney, AUS; Barstow, CA) to determine the consequences of local meteorological climates on PV-EC CO2R product output, recording a maximum ethylene output of 18.5 tonne/yr at Barstow. Overall, this model presents a critical tool for streamlining the translation of experimental solar-driven electrochemical research to real-world implementation.

Hollow-Structured Co-MoSx/Graphene Trifunctional Electrocatalyst for Self-Powered Hydrogen Production System.

Developing a single electrocatalyst that can facilitate both rechargeable aqueous metal-air batteries and water splitting has become a crucial focus in renewable-energy technologies. This necessitates addressing the three distinct electrocatalytic reactions: the electrochemical oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Despite significant efforts, the creation of a alkaline medium based trifunctional catalyst with high activity at a low cost has proven to be a considerable challenge. Currently, Pt and its alloys have been considered as the most active catalysts for the ORR and HER, whereas noble-metal oxides such as IrO2 and RuO2 are considered as the golden standards of OER catalyst. However, noble-metals based catalyst have been suffered from their high cost, limited reserves in the Earth’s crust, and poor electrocatalytic stability. Moreover, these noble metals face challenges in simultaneously exhibiting trifunctional catalytic activity for ORR, OER, and HER. In recent study, Transiton metal sulfides(TMSs) have great attraction as trifunctional catalyts due to their eqrth abudance, tunnable band structure, and crystal structure. especially, one of widely used TMCs is MoS2 because of their Pt-like high catalytic activity for HER as well as thermodynamic electrochemical stability and rich catalytic sites in the planar nature. However, the most stable 2H (hexagonal) phase MoS2 suffers from poor electrical conductivity, low wettability, and aggregation indced reducing active catalytic sites and resulting high resistance. 2H MoS2 also shows poor activity for OER and ORR, thereby hampering its practical applications as trifunctional catalyst. To overcome this threshold, various strategies have been conducted to improve their electrochemical charateristics, such as defect engineering, heterojunction foramtion, phase transform and integrating porosity control. However, commonly considered method to synthesis requires complex multi-steps with high temperature, vaccum system, explosive gas, and toxic etchant.In this study, we successfully synthesized the homogeneous growth of a Co-based nanometer-scale metal-organic framework (MOF) on graphene oxide at room temperature. Furthermore, a facile one-pot solvothermal method was employed to synthesize Co-MoSx/Graphene, which consists of a hollow, heterogeneous bimetallic sulfide (Co3S4/MoS2 with Co-S-Mo bonding) within a sandwiched graphene/MoS2 layer, demonstrating superior trifunctional activity and stability. Incorporating a conductive graphene layer between MoS2 layers is an effective strategy for not only realizing high electrical conduction to MoS2 layers, but also increasing MoS2 interlayer spacing for high ion accessibility. Besides, a variety of techniques, including Cs-corrected scanning transmission electron microscope (Cs-STEM), X-ray diffraction(XRD), and X-ray absorption spectroscopy (XAS), are used to confirm the atomic configurations of Co-MoSx/Graphene structure and morphologies. Also, Raman, Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) were conducted to investigating the binding structure and chemical states. Furthermore, The internal electric field (IEF) within heterojunction, which induced from the differing electron density of the bimetallic species and the sandwiched graphene are contribute not only electron density structure optimization for enhancing reaction kinetics but also accelerating electron-hole exchange. The IEF in the microporous-heterostructure accelerates the diffusion of reaction intermediate with sufficient mass transport and facilitates a Graphene/MoS2-to-Co-MoSx pathway for enhancing redox kinetics of sluggish OER and ORR. Consequently, the OER and ORR-inactive MoS2, HER, and ORR-inactive Co3S4, along with less catalytically effective graphene, demonstrate outstanding performance when combined in the bimetallic sulfide based highly active heterojunctional structure. To investigate the electrochemical catalytic properties of Co-MoSx/Graphene, Rotating disk electrode(RDE) was used with three electrode measurment. The presence of MoS2/Graphene on Co3S4 and Co-MoSx bonding species in Co-MoSx/Graphene enhances the alkaline electrochemical catalytic activity by reducing overpotential and Tafel slopes(220 mV, 110 mV dec-1 in HER and 320 mV, 55.8 mV dec-1 in OER) under 1M KOH solution. Moreover, the ORR performance was evaluated by using Koutecky-Levich (K-L) Plot with different rotating speeds under 0.1M KOH. The electron transfer number (n) is closed theoretical value of 4.0 also shows outstanding performance of the onset potential, half-wave potential and kinetic current density (0.88 V, 0.67 V, and 10.4 mA cm-2), which is comparable that of Pt/C (0.92 V, 0.8 V, and 10.3 mA cm-2). Furthermore, Co-MoSx/G based rechargeable Zinc-Air battery achieve over 85% of theoretical zinc utilization efficiency and 1.4 times higher power density than a Pt/C + RuO2 air cathode based system. We believe that this work could provide a rational strategy for achieve trifunctional electrocatalyst and high performance self-powered hydrogen production system.This research was supported by the National Research Foundation of Korea (2022M3H4A1A04096482, RS-2023-00229679) funded by the Ministry of Science and ICT.

Functionalization of CO2-Derived Carbon Support as a Pathway to Enhancing the Oxygen Reduction Reaction Performance of Pt Electrocatalysts

Functionalization of CO₂-Derived Carbon Support as a Pathway to Enhancing the Oxygen Reduction Reaction Performance of Pt Electrocatalysts

A Machine Learning‐Enhanced Framework for the Accelerated Development of Spinel Oxide Electrocatalysts

AbstractThe surging demand for sustainable energy has spurred intensive research into electrochemical conversion devices such as fuel cells, water splitting, and metal‐air batteries. The performance of oxygen electrocatalysts significantly impacts overall electrochemical efficiency. Recently, spinel oxides (AB2O4) have emerged as promising candidates; however, the scarcity of prior studies underscores the need for a thorough and comprehensive exploration. This study presents a computational framework that integrates machine learning and density functional theory (DFT) calculations for the systematic screening of 1240 spinel oxides. The data scarcity is addressed while enhancing prediction accuracy. Selected candidates are identified to outperform the benchmarking perovskite oxide. Additionally, their potential as mixed ionic and electronic conductors with a 3D network of ion diffusion pathways is highlighted. To further enhance the understanding and prediction of stability, catalytic activity, and reaction mechanisms, a new undemanding descriptor is introduced: the covalency indicator. This study offers a design principle for the development of high‐performance spinel oxide oxygen electrocatalysts.

Probing Electrocatalytic Synergy in Graphene/MoS2/Nickel Networks for Water Splitting through a Combined Experimental and Theoretical Lens.

The development of low-cost and active electrocatalysts signifies an important effort toward accelerating economical water electrolysis and overcoming the sluggish hydrogen or oxygen evolution reaction (HER or OER) kinetics. Herein, we report a scalable and rapid synthesis of inexpensive Ni and MoS2 electrocatalysts on N-doped graphene/carbon cloth substrate to address these challenges. Mesoporous N-doped graphene is synthesized by using electrochemical polymerization of polyaniline (PANI), followed by a rapid one-step photothermal pyrolysis process. The N-doped graphene/carbon cloth substrate improves the interconnection between the electrocatalyst and substrate. Consequently, Ni species deposited on an N-doped graphene OER electrocatalyst shows a low Tafel slope value of 35 mV/decade at an overpotential of 130 mV at 10 mA/cm2 current density in 1 M KOH electrolytes. In addition, Ni-doped MoS2 on N-doped graphene HER electrocatalyst shows Tafel slopes of 37 and 42 mV/decade and overpotentials of 159 and 175 mV, respectively, in acidic and alkaline electrolytes at 10 mA/cm2 current density. Both these values are lower than recently reported nonplatinum-group-metal-based OER and HER electrocatalysts. These excellent electrochemical performances are due to the high electrochemical surface area, a porous structure that improves the charge transfer between electrode and electrolytes, and the synergistic effect between the substrate and electrocatalyst. Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations demonstrate that the Ni hydroxide species and Ni-doped MoS2 edge sites serve as active sites for OER and HER, respectively. Finally, we also evaluate the performance of the HER electrocatalyst in commercial alkaline electrolyzers.

Studying impact of cobalt content on electrocatalytic activity of Cu-Co-P coating with dendrite-like architectures for hydrogen production

The aim of this study was to enhance the electrocatalytic performance of the electrodeposited Cu-Co-P coating by adjusting the Co content. SEM images revealed that the presence of Co contributed to the formation of a nano/micro dendritic morphology. The electrocatalyst performance improved as the Co content increased. Specifically, the Cu-Co-P/60@NF electrode only required an overpotential of 102 mV (versus reversible hydrogen electrode (RHE)) at a current density of −10 mA/cm2. This electrode exhibited the lowest charge transfer resistance, promoting faster charge transfer at the electrocatalyst/electrolyte interface. The increase in electroactivity for the hydrogen evolution reaction (HER) with a higher Co content can be attributed to two factors: the construction of the porous nano/micro dendritic structure and the synergistic effect between P, Cu, and Co elements, which is influenced by their amounts in the coating. Moreover, this electrode demonstrated satisfactory stability for 14 hours of electrolysis at −100 mA/cm2. In a two-electrode system, it only required a cell voltage of 1.57 V to achieve a current density of 10 mA/cm2. As a result, the Cu-Co-P/60@NF electrode could hold promise as a cost-effective alternative to noble metal-based electrocatalysts.

Plasmon-enhanced electrocatalytic ethanol oxidation over Au@Pd nanostars

Hybrid noble-metal nanostructures, which integrate plasmonic characteristics and electrocatalytic performance, have garnered significant interest recently. In this study, Au@Pd nanostars were synthesized and employed as an advanced electrocatalyst for the ethanol oxidation reaction (EOR), which suffers from the kinetic limitations of the anodic half-reaction of direct ethanol fuel cells. Leveraging the superior surface plasmon resonance (SPR) property of Au nanostars, the synthesized Au@Pd nanostars exhibited superior plasmon-enhanced EOR activity of 4191.63 A g−1 under laser illumination, noting a 9.40-fold increase compared to dark conditions (445.99 A g−1). The influences of Pd loading and laser power on EOR activity were explored. The impact of Pd loading on EOR activity demonstrates a volcano-shaped correlation, where optimal Pd coverage enhances catalysis but excessive amounts dampen SPR performance, crucial for maximizing EOR activity. Within a specified range, EOR activity linearly increases with laser power due to its influence on SPR performance. Mechanistic investigation suggests the critical roles of photothermal effect and hot carriers’ separation in boosting EOR kinetics. The repeated experiments show little difference, ensuring the accuracy and reproducibility of the reported activity of Au@Pd nanostars for EOR. During the long-term stability estimation, the Au@Pd nanostars display the best durability over three electrocatalysts. Overall, our findings highlight the potential of plasmon-enhanced catalysis in advancing the performance of electrocatalysts for EOR and other conventional electrocatalytic reactions.

Synthesis and Catalytic Performance of Bimetallic Oxide-Derived CuO-ZnO Electrocatalysts for CO2 Reduction.

Steering the selectivity of electrocatalysts toward the desired product is crucial in the electrochemical reduction of CO2. A promising approach is the electronic modification of the catalyst's active phase. In this work, we report on the electronic modification effects on CuO-ZnO-derived electrocatalysts synthesized via hydrothermal synthesis. Although the synthesis method yields spatially separated ZnO nanorods and distinct CuO particles, strong restructuring and intimate atomic mixing occur under the reaction conditions. This leads to interactions that have a profound effect on the catalytic performance. Specifically, all of the bimetallic electrodes outperformed the monometallic ones (ZnO and CuO) in terms of activity for CO production. Surprisingly, on the other hand, the presence of ZnO suppresses the formation of ethylene on Cu, while the presence of Cu improves CO production of ZnO. In situ X-ray absorption spectroscopy studies revealed that this catalytic effect is due to enhanced reducibility of ZnO by Cu and stabilization of cationic Cu species by the intimate contact with partially reduced ZnO. This suppresses ethylene formation while favoring the production of H2 and CO on Cu. These results show that using mixed metal oxides with different reducibilities is a promising approach to alter the electronic properties of electrocatalysts (via stabilization of cationic species), thereby tuning the electrocatalytic CO2 reduction reaction performance.

Oxygen-deficient annealing boosts performance of CoNiFe oxide electrocatalyst in oxygen evolution reaction

Mixed oxides of transition metals have emerged as promising catalysts for the oxygen evolution (OER) reaction in alkaline water electrolysis. Since OER is significantly slower than hydrogen evolution, developing stable and easily accessible materials that effectively promote OER is one of the keys to improving overall efficiency. In this context, we present a promising method for preparing Co-Ni-Fe oxides which is based on a straightforward sol–gel procedure. Key to success is a thermal treatment under oxygen-deficient atmosphere, which renders superior electrocatalytic properties compared to a treatment under reductive and aerobic conditions, respectively. Attractive performance characteristics are thereby obtained, e.g., a η10 value of 291mV and a Tafel slope of 32 mV dec−1. The impact of the annealing conditions on the material properties has been elaborated using cyclic voltammetry, impedance spectroscopy, and structural analyses. Stability and strong performance under practical conditions was confirmed in long-term studies using an AEM electrolyzer.