Benchmark Catalyst Research Articles

Bamboo-derived aerogel with atomically dispersed Co as a high-performance bifunctional electrocatalyst for durable zinc-air batteries

The development of highly efficient and durable bifunctional electrocatalysts is crucial for rechargeable zinc-air batteries, which have garnered significant attention as a promising sustainable energy storage technology. Herein, a novel Co-N-C-1050 catalyst is synthesized using a high-temperature gas transport method, where high purity cobalt powder and bamboo biomass aerogel are treated with ammonia gas at 1050 °C. The resulting catalyst exhibits a 3D interconnected porous network composed of dense carbon fibers, which atomically dispersed Co, N, and C elements are uniformly distributed. The synergistic integration of highly active Co single atoms and N-doped 3D carbon fiber aerogel enables Co-N-C-1050 to demonstrate excellent bifunctional electrocatalytic performance for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), comparable to commercial Pt/C and RuO2 catalysts. This catalyst has a half-wave potential of 0.842 V for ORR and a potential of 1.472 V at 10 mA cm−2 for OER, outperforming N-C-1050 and benchmark catalysts. A zinc-air battery is driven by Co-N-C-1050 achieves a high power density of 135 mW/cm2 and exceptional stability over 138 h of charge/discharge cycling, surpassing the higher-cost Pt/C + RuO2 catalyst. This biomass aerogel based single-site Co-N-C catalyst offers a promising approach for developing high-efficiency and long-cycle-life zinc-air batteries.

Tailoring Hydrogen Adsorption via Charge Transfer at Bimetallic Cr0.48Ru0.52 Alloy Nanoparticles Decorated on Carbon Nanofiber for Enhanced Hydrogen Evolution Catalysis

Designing and synthesizing highly efficient and stable electrocatalysts for the hydrogen evolution reaction (HER) is crucial for the practical and large-scale application of hydrogen sources. Recent research has focused on tuning the electronic structure of electrocatalysts to achieve optimal HER activity, with particular emphasis on interfacial engineering to induce electron transfer and optimize HER kinetics. In this study, as part of research into heterointerface engineering, bimetallic Cr0.48Ru0.52 alloy nanoparticles decorated on carbon nanofibers (Cr0.48Ru0.52/CNFs) were fabricated through a simple electrospinning and post-calcination process to serve as an efficient alkaline HER catalyst. The Cr0.48Ru0.52/CNFs demonstrated exceptional electrocatalytic HER performance, with an overpotential of only 13 mV at −10 mA cm−2 and a Tafel slope of 60.8 mV dec−1, indicating high catalytic activity compared to commercial benchmark catalysts (i.e., Ru/C and Pt/C). First-principles density functional theory calculations support these results, revealing that Cr0.48Ru0.52 balances proton reduction (Volmer step) and H* desorption (Tafel/Heyrovsky step) processes during electrocatalysis, as evidenced by the near-zero hydrogen adsorption (ΔGH*) value (ca. −0.11 eV). Therefore, this study highlights that Cr0.48Ru0.52/CNFs, with noble Ru comprising only half of the total metal content, can promote optimal HER kinetics under alkaline condition.

P-functionalization of Ni Fe − Electrocatalysts from Prussian blue analogue for enhanced anode in anion exchange membrane water electrolysers

Efficient hydrogen generation from water-splitting is widely acknowledged as a priority route to promote the hydrogen economy. Anion exchange membrane water electrolyzers (AEMWE) offer multiple advantages in improving performance and minimizing the cost limitations of current electrolysis technologies. However, the persistence of issues related to the limited electrocatalytic activity of such materials and their poor stability under operating conditions makes developing highly active, stable, platinum-group-metal-free electrocatalysts for oxygen evolution reaction (OER) necessary.We report the development of Prussian blue analogues (PBA)-derived NiFe-based electrocatalysts through a mild aqueous phase precipitation method, followed by thermal stabilization and phosphorus doping. The formation of the NiFe-PBA-precursor with a framework nanocubic Ni(II)[Fe(III)(CN)6]2/3 structure was confirmed by X-ray diffraction, scanning electron microscopy, and inductively coupled plasma analysis. The NiFe-PBA-precursor was subjected to thermal stabilization and phosphorus doping to provide the material with enhanced OER catalytic activity and stability. The existence of OER active sites based on NiFe and NiFeP has been revealed by transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization in a three-electrode cell configuration in a 1 M KOH electrolyte. NiFe-PBA and NiFeP-PBA were assembled at the anode side of an AEMWE, resulting in an excellent electrochemical performance both in terms of current density at 2.0 V using 1 M KOH (1.21 A cm−2) and durability, outperforming the benchmark catalyst.

Engineering medium-entropy alloy nanoparticle nanotubes for efficient oxygen reduction

Fuel cells, as promising energy conversion devices, realize the direct conversion of hydrogen fuel chemical energy into electrical energy. The kinetics of cathodic oxygen reduction reaction (ORR) is slow and plays a decisive role in the output efficiency of fuel cells. Platinum catalysts have been commercialized, but their high cost, relatively low catalytic activity and poor cycling durability limit the development of fuel cells. The introduction of non-platinum components is an effective strategy to minimize the cost and maximize the activity. In this study, PtPdCu medium entropy alloy nanoparticle nanotubes (PtPdCu MEANPTs) that demonstrate high catalytic activity and long durability are presented. Combined with density functional theory calculations, the introduction of Pd and Cu modulates surface electronic structure and optimizes the oxygen adsorption energy, thus enhancing the catalytic activity. The 0D/1D hybrid structure exposes more surface sites and inhibits particle maturation. The atomic migration and rearrangement are emerged during the initial stage of potential cycling process, induing a palladium-rich outer layer and preventing the oxidation of platinum atoms. The best-performing Pt24Pd28Cu48 MEANPTs deliver the impressive ORR activity (1.42 A/mgPt at 0.9 V vs. RHE, which is 6.17 times that of commercial Pt/C) and durability (retaining 2.87 times the initial activity of benchmark catalyst after 30,000 potential cycles). Theoretical calculations have confirmed the regulation of alloying on the surface oxygen affinity and revealed the true active sites on the catalyst surface. This work explores the research direction of platinum-based multi-element catalysts with low platinum content and high catalytic activity.

Oxygen-Deficient Ruthenium Oxide for Selective Oxygen Evolution in Additive-Free Brine Electrolysis

Here, low-crystalline ruthenium oxide (S-RuO x ) with abundant oxygen vacancies was synthesized, after which its activity and selectivity toward oxygen evolution reaction (OER) in additive-free brine solution were compared with those of commercial ruthenium(IV) dioxide (C-RuO2), a benchmark catalyst for OER in an alkaline electrolyte. S-RuO x delivered a current density of 10 mA cm−2 at a significantly low overpotential (465 mV) in a 0.5 M NaCl solution without requiring an alkali. The estimated Faradaic efficiency toward chloride oxidation reaction (COR), FE(COR), was 2%, and exceptional OER was achieved without generating chlorine oxide species. This sharply contrasts the fact that C-RuO2 required an overpotential of 525 mV to generate 10 mA cm−2, where the FE(COR) was 59%. The activity and selectivity toward OER decreased after reducing the oxygen vacancies by sintering S-RuO x at different temperatures. S-RuO x continued to generate 10 mA cm−2 in 0.5 M NaCl solution for ≥60 h while maintaining the increasing potential at <30 mV. However, FE(COR) increased from a few percent for 20 h to 34% probably because of an irreversible decrease in vacancies. Notably, the addition of an alkali or a buffer could only enhance OER.

CO2 methanation on Ni/Y2O3 Catalysts: The effects of preparation procedure and cerium oxide promotion

Present paper reports on the CO2 methanation (CME) performance of novel Ni catalysts supported on yttria, ceria, and ceria-doped yttria carriers. Catalysts were synthesized using incipient wetness impregnation and precursor nitrate co-decomposition. These systems outperformed on a mass-specific basis an industrial Ni/alumina benchmark catalyst. In addition, this work examines in details the impact of both the preparation procedure and the Ni-content on the CME activity both in terms of the reaction rate and the apparent activation energy. Our research demonstrates that Y2O3 is an effective catalytic support promoting stability and activity of the catalysts. CeO2–doping further improves activity, remarkably with little to no penalty to the thermal stability of the catalysts. Comparison of the performance of a conventional IWI-synthesized Ni-catalyst with a counterpart obtained via a co-decomposition route, demonstrated an advantage of the latter. Our findings suggest Ni-CeO2/Y2O3 prepared via co-decomposition may be advised as the active and stable catalysts for CME applications.

Elevating Oxygen Evolution using Iron Phthalocyanine Infused Vanillic acid Electrocatalyst.

Oxygen evolution reaction (OER) is the bottle neck step in water splitting reaction towards the realization of hydrogen based clean energy production and storage. Metal air batteries and polymer electrolyte membrane fuel cells (PEMFC) are the alternative green energy systems that utilise O2 and H2 in the production of continuous and high energy output without the utilization of carbon based fuels which are the major sources of pollution. Transition metal based N4 organics are explored extensively as oxygen electrocatalysts i. e., OER and oxygen reduction reaction (ORR) catalysts because of their ease of synthesis, tuneable properties, low cost and high performance with long term stability. Here, vanillic acid functionalized iron phthalocyanine (FeVAPc) was synthesised and characterised by various spectroscopic techniques. The novel FeVAPc exhibited good thermal stability and was coated on Ni foam for OER studies. The scanning electron microscopy images showed net-work like surface morphology and the X-ray photoelectron spectroscopy indicated the presence of Fe in +3 oxidation state. The Ni/FeVAPc demonstrated excellent electrocatalytic activity for OER with overpotential of 312 mV at 10 mA.cm-2 current density in 1.0 M KOH electrolyte. The designed organic based catalyst exhibited lesser Tafel slope value which is nearer to the benchmark catalyst, IrO2. The proposed catalyst exhibited good stability as phthalocyanines are highly stable and do not undergo decomposition even in strong acidic and basic corrosive media. Integration of FeVAPc onto the Ni foam resulted in higher mass activity, lower charge transfer resistance, high active surface area leading to enhanced conductivity and activity. The fabricated Ni/FeVAPc is an appropriate cost-effective, efficient and stable catalyst for OER towards industrial applications.

Strong interaction heterointerface of NiFe oxyhydroxide/cerium oxide for efficient and stable water oxidation

NiFe oxyhydroxides (NiFeOxHy) are the benchmark catalysts for alkaline oxygen evolution reaction (OER), however, it is still challenging for these electrocatalysts to achieve both high activity and long-term stability. Herein, we demonstrate that strong interaction heterointerface of NiFeOxHy/cerium oxide (CeO2) can control the reconstruction process of NiFeOxHy and the reaction pathway of OER, which simultaneously improves the activity and stability of the catalyst. Interestingly, after electrochemical activation, with and without CeO2, NiFeOxHy oxyhydroxides exhibit completely different structures, with the former being uniformly distributed ultrafine nanosheets and the latter being spherical agglomerates of larger sized nanosheets. The strong heterointerface interaction induces the electrons of Ni and Fe to shift to Ce. The optimized catalyst exhibits a low overpotential of 240 mV at 100 mA cm−2 with the durability over 2000 h at 200 mA cm−2. The OER mechanism studies indicate that NiFeOxHy/CeO2 heterointerface follows lattice oxygen oxidation mechanism with accelerated kinetics.

Surface‐Segregated IrCo Nanoparticles on CoO Nanosheets with Ultralow Ir Loading for Efficient Acidic Water Splitting

AbstractIrO2 is the benchmark catalyst for acidic oxygen evolution reaction (OER), however, the high cost and low earth abundance hinder its large‐scale application. Herein, surface‐segregated IrCo nanoparticles on CoO nanosheets with a strong electronic interaction are synthesized through the ion exchange‐pyrolysis method. The resulting IrCo−CoO heterostructures, containing an ultra‐low Ir content of 4.73 wt %, demonstrate exceptional performance in the acidic OER. The catalyst exhibits a low overpotential of 270 mV at a current density of 10 mA cm−2 and remarkable stability, with noticeable activity decay observed only after 140 hours of continuous operation. These results surpass most reported Ir‐based electrocatalysts. Specifically, the mass activity at the overpotential of 300 mV for the IrCo−CoO catalyst reaches 124.52 mA mgIr−1, which is 20 times higher than that of commercial IrO2. Furthermore, we constructed a home‐made overall water splitting cell utilizing IrCo−CoO heterostructures as both anode and cathode electrodes, achieving a current density of 10 mA cm‐−2 at a voltage of 1.51 V. Our findings present a promising strategy for designing high‐efficient catalysts with significantly reduced noble metals loading.

Electrodeposited manganese carbonate as an electrocatalyst for hydrogen evolution reaction in acidic medium

The electrolysis of water is the key method for hydrogen production but the high overpotential necessitates electrocatalysts. Traditionally, Pt is used, but it is scarce and costly. Herein, MnCO3 is unveiled as an electrocatalyst for the production of hydrogen. MnCO3 is electrodeposited onto pencil graphite by chronoamperometric method and confirmed by XRD and vibrational spectroscopic studies. MnCO3 electrodeposited for 15 min at 2 V demonstrates a good HER activity (overpotential of 123 mV to reach 10 mA cm−2) in 0.5 M H2SO4 with a Tafel slope of 79 mV dec−1. In addition, MnCO3 exhibited good stability during continuous operation (over 3000 cycles and 14 h). Though MnCO3 requires higher overpotential than the benchmark catalyst (Pt/C) to reach 10 mA cm−2, it outperforms Pt/C at higher current density (≥75 mA cm−2) demonstrating that MnCO3 could be used as an electrocatalyst to produce H2 at a high rate from acidic medium.

Unlocking the potential: strategic synthesis of a previously predicted pyrazolate-based stable MOF with unique clusters and high catalytic activity.

The metal-organic framework (MOF) constructed from [Co4Pz8] clusters (Pz = pyrazolate) and 1,3,5-tris(pyrazolate-4-yl) benzene (BTP3-) ligands was structurally predicted many years ago, and expected to be a promising candidate for various applications owing to its unique clusters and highly open 3D framework structure. However, this MOF has not been experimentally prepared yet, despite extensive efforts were made. In this work, we present the successful construction of this MOF, hereinafter referred to as BUT-124(Co), by adopting a two-step synthesis strategy, involving the initial construction of a template framework (BUT-124(Cd)) followed by a post-synthetic metal metathesis process. The effects of various cobalt sources and solvents were systematically investigated, and an innovative stepwise metathesis strategy was employed to optimize the exchange rates and the porosity of the material. BUT-124(Co) demonstrates high catalytic activity in the oxygen evolution reaction (OER), achieving a competitive performance with an overpotential of 393 mV at a current density of 10 mA cm-2, and also affords remarkable long-term stability during potentiostatic electrolysis in 1 M KOH solution, surpassing the durability of many benchmark catalysts. This work not only introduces a novel MOF material with promising properties but also exemplifies a strategic synthesis approach for pyrazolate-based MOFs, paving the way for advancements in diverse application fields.

Lanthanum Transition-Metal Sulfide Electrocatalysts for Overall Water Splitting

Hydrogen has been identified as a sustainable energy source for the future with the potential of replacing fossil fuels due to its high gravimetric energy density and zero carbon emissions. Water electrolysis is a promising approach to the clean production of pure hydrogen, however, the benchmark catalysts of the half reactions of water electrolysis are noble-metal based, which limit the application of this technique.1 As well, the high energy barrier and sluggish kinetics of the oxygen evolution reaction limit the efficiency of the system. Therefore, it is crucial to develop robust, stable, and cost-effective materials for water electrolysis to be scalable. Lanthanum transition-metal oxide electrocatalysts have been pursued in the past for water splitting due to the high abundance of lanthanum and transition metals.2 However, these catalysts suffer from low conductivity and inherent instability towards oxygen evolution. Binary sulfides, selenides, and phosphides have also been pursued,3 but the compositional space of these materials is limited. Ternary sulfides offer a wider compositional space that allows fine-tuning for optimal performance. As a result, we have pursued the synthesis and application of the relatively unexplored ternary chalcogenides, LaMS3 (M = Ni, Co, Fe, Mn) towards water electrolysis. The efficiency of water electrolysis and stability of the materials have been tested with linear sweep voltammetry, galvanostatic measurements, and electrochemical impedance spectroscopy. We found these materials to be active towards both the hydrogen and oxygen evolution reactions, in acidic and alkaline conditions, respectively, with the catalysts exhibiting an activity trend where LaNiS3 > LaCoS3 > LaFeS3 > LaMnS3. For HER, LaNiS3 exhibits an overpotential of 340 mV at 10 mAcm-2 with a Tafel slope of 79 mV/decade. For OER, an overpotential of 373 mV at 10 mAcm-2 and a low Tafel slope of 48 mV/decade are observed. In addition, LaNiS3 proved to be highly stable with minimal change in potential over a period of 18 hours. The high activity and stability of LaNiS3 towards both half reactions of water electrolysis make it a promising candidate for a bifunctional water splitting electrocatalyst.References Wang, S.; Lu, A.; Zhong, C.-J. Hydrogen Production from Water Electrolysis: Role of Catalysts. Nano Convergence 2021, 8 (1), 4.Dias, J. A.; Andrade, M. A. S.; Santos, H. L. S.; Morelli, M. R.; Mascaro, L. H. Lanthanum‐Based Perovskites for Catalytic Oxygen Evolution Reaction. ChemElectroChem 2020, 7 (15), 3173–3192.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 Catal. 2016, 6 (12), 8069–8097.

A General Descriptor for Single‐Atom Catalysts with Axial Ligands

AbstractDecoration of an axial coordination ligand (ACL) on the active metal site is a highly effective and versatile strategy to tune activity of single‐atom catalysts (SACs). However, the regulation mechanism of ACLs on SACs is still incompletely known. Herein, we investigate diversified combinations of ACL‐SACs, including all 3d–5d transition metals and ten prototype ACLs. We identify that ACLs can weaken the adsorption capability of the metal atom (M) by raising the bonding energy levels of the M−O bond while enhancing dispersity of the d orbital of M. Through examination of various local configurations and intrinsic parameters of ACL‐SACs, a general structure descriptor σ is constructed to quantify the structure–activity relationship of ACL‐SACs which solely based on a few key intrinsic features. Importantly, we also identified the axial ligand descriptor σACL, as a part of σ, which can serve as a potential descriptor to determine the rate‐limiting steps (RLS) of ACL‐SACs in experiment. And we predicted several ACL‐SACs, namely, CrN4‐, FeN4‐, CoN4‐, RuN4‐, RhN4‐, OsN4‐, IrN4‐ and PtN4‐ACLs, that entail markedly higher activities than the benchmark catalysts of Pt and IrO2 for oxygen reduction reaction and oxygen evolution reaction, respectively, thereby supporting that the general descriptor σ can provide a simple and cost‐effective method to assess efficient electrocatalysts.

Alkaline hydrogen evolution reaction catalyzed by atomically dispersed ruthenium on phosphorus-nitrogen co-doped porous carbon

Exploring high-efficiency catalyst toward hydrogen evolution reaction (HER) for sustainable hydrogen production is critical for building a forthcoming hydrogen economy. Atomically dispersed catalysts have shown great promises for catalyzing HER yet further fine-tuning the coordination chemical environment to boost the performance is still challenging. Herein, we report the synthesis and electrocatalytic HER application of Ru single atoms dispersed in P, N co-doped porous carbon (Ru SAs@PNC). Spherical aberration corrected scanning transmission electron microscope (AC-STEM) analysis revealed the formation of atomically dispersed Ru single atoms. The as-prepared Ru SAs@PNC catalyst showed excellent HER activity in 1 M KOH, evidenced by a small overpotential of 21 mV @ 10 mA cm−2 and a low Tafel slope of 31 mV dec−1, both of which are comparable to the Pt/C benchmark catalyst. It also exhibited great durability for long-time operation, as demonstrated by negligible overpotential increase in the 50 h E-t test, and outperformed stability in the accelerated durability test. Such excellent HER performance is mainly attributed to the N, P co-doped chemical coordination environment that differs from most widely reported solely nitrogen-coordinated Ru single atoms.

Evaluating the impact of iron impurities in KOH on OER performance of BaNiO3 single crystals using scanning electrochemical cell microscopy

Understanding the oxygen evolution reaction (OER) electrocatalysis requires a careful understanding of the surface and activity evolution of well-defined materials. An especially promising candidate is the BaNiO3 hexagonal perovskite, matching strides with benchmark catalysts such as Ba0.5Sr0.5Co0.8Fe0.2O3–δ. Here, we conducted a structural and electrochemical analysis of BaNiO3 single crystals to assess the influence of iron impurities in KOH electrolyte on their OER performance. We used scanning electrochemical cell microscopy (SECCM) for precise measurements on BaNiO3 single crystals in the absence of carbon additives. Cyclic voltammetry (CV) revealed that the presence of iron consistently enhanced the OER current with subsequent cycles, indicating a dynamic improvement in BaNiO3's electrochemical activity. Conversely, in iron-free KOH electrolyte, performance diminished with cycling. These findings not only underscore the critical necessity of KOH purification for BaNiO3 electrochemical studies but also showcase SECCM's unparalleled ability to offer insights into the electrochemical evolution of individual entities such as single crystals. This makes it a powerful operando tool for evaluating forthcoming single crystals, thereby aiding in the design of superior catalysts for OER reactions.

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO2 or Al2O3. NH3-TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO2 gives softer coke and increases cumulative benzene yields by 25 %, while Al2O3 strongly decreases yields. H2-TPR and UV–visible and Raman spectroscopy show how the overcoats redisperse the MoOx precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27Al-MAS NMR, MoOx redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Overall, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

Atmospheric oxygen plasma-activated novel multicomponent transition metal phosphides (MnCoCu–P) for enhanced electrocatalytic water splitting to green hydrogen production: A universal catalyst across various pH electrolytes

Hydrogen (H2) is widely acknowledged as a promising, sustainable, and environmentally friendly energy carrier, offering numerous environmental benefits over conventional fossil fuels. However, the advancement of this technology is severely hindered by the scarcity of effective and robust catalysts for hydrogen evolution (HER) and oxygen evolution (OER) reactions activity. This study marks the inaugural fabrication of a hybrid tri-metallic electrocatalyst, termed MnCoCu–P, through hydrothermal synthesis. Subsequently, the catalyst undergoes atmospheric O2 plasma surface activation, aiming to amplify the efficiency of water splitting. The novel atmospheric O2 plasma-activated MnCoCu–P electrode outperforms the reported classic metal phosphides, and it outperformed the compared commercial Pt/C and RuO2 benchmark catalysts with outstanding performances of 0.488 and 1.20 V towards HER and OER at 1000 mA/cm2, respectively. Additionally, the MnCoCu–P (5 min) catalyst Faradic efficiency was calculated under alkaline conditions in 1.0 M KOH, and both the produced gas H2 and O2 match the theoretical and experimental calculated values well, indicating a high efficiency of almost 100%. In the 2-E system, MnCoCu–P (5 min)‖MnCoCu–P (5 min) demonstrated remarkable performance by attaining a current density of 1000 mA/cm2 at low total cell voltages of 1.93 V and outperforming the benchmark Pt/C‖RuO2 electrode system. On the other hand, the MnCoCu–P electrode possesses excellent activity under industrial conditions at 6.0 M @ 60 °C exhibited 1.89 V at 1000 mA/cm2 and performs well in natural water systems. Moreover, the 5 min O2 plasma-treated MnCoCu–P‖MnCoCu–P electrodes showed improved activity in all the pH solutions which makes it one of the potential candidates for commercial application in the future.

A General Descriptor for Single-Atom Catalysts with Axial Ligands.

Decoration of an axial coordination ligand (ACL) on the active metal site is a highly effective and versatile strategy to tune activity of single-atom catalysts (SACs). However, the regulation mechanism of ACLs on SACs is still incompletely known. Herein, we investigate diversified combinations of ACL-SACs, including all 3d-5d transition metals and ten prototype ACLs. We identify that ACLs can weaken the adsorption capability of the metal atom (M) by raising the bonding energy levels of the M-O bond while enhancing dispersity of the d orbital of M. Through examination of various local configurations and intrinsic parameters of ACL-SACs, a general structure descriptor σ is constructed to quantify the structure-activity relationship of ACL-SACs which solely based on a few key intrinsic features. Importantly, we also identified the axial ligand descriptor σACL, as a part of σ, which can serve as a potential descriptor to determine the rate-limiting steps (RLS) of ACL-SACs in experiment. And we predicted several ACL-SACs, namely, CrN4-, FeN4-, CoN4-, RuN4-, RhN4-, OsN4-, IrN4- and PtN4-ACLs, that entail markedly higher activities than the benchmark catalysts of Pt and IrO2 for oxygen reduction reaction and oxygen evolution reaction, respectively, thereby supporting that the general descriptor σ can provide a simple and cost-effective method to assess efficient electrocatalysts.

Synthesis and characterization of hydrophobic nickel catalyst supported on different oxides for continuous liquid phase catalytic exchange reaction

Hydrophobic Ni catalysts supported on three metal oxides coated with PTFE namely Ni/SiO2/PTFE, Ni/Cr2O3/PTFE, and Ni/Al2O3/PTFE were used in liquid-phase catalytic exchange (LPCE) reactions to enrich hydrogen isotope and produce deuterium oxide (heavy water). Wet impregnation method was employed to prepare the Ni/SiO2, Ni/Cr2O3, and Ni/Al2O3 before PTFE coating. The as prepared catalysts were characterized using different characterization techniques and their performances were evaluated in LPCE reaction using a continuous reactor. The performance evaluation based on the D2O yield can be ranked as Ni/Al2O3/PTFE > Ni/Cr2O3/PTFE > Ni/SiO2/PTFE > Ni/PTFE. The catalysts’ performances are strongly associated with the crystallite size, particle size, hydrophobicity, surface area, pore size, and metal-support interaction. Since isotope exchange requires a dry catalyst surface, the catalyst’s hydrophobicity plays a crucial role. In addition, the catalyst support improves the LPCE reaction efficiency, as the most efficient catalyst, Ni/Al2O3/PTFE, yielded 1220 ppm D2O, compared to 520 ppm for the benchmark catalyst, Ni/PTFE. The characterization results reveal that Ni/Al2O3/PTFE outperformed the other catalysts due to its low crystallite size (D = 23.04 nm), high hydrophobicity (WCA = 139.23°), higher surface area (16.31 m2g−1), small pores (pore size = 6.18 nm), and lowest average Ni particle size (40.89 nm).

Attaining Substantially Enhanced Oxygen Evolution Reaction Rates on Ni Foam Catalysts in a Gas Diffusion Electrode Setup

Water electrolysis plays a central role in the transition to a fossil‐free society, but there are significant challenges to overcome in order to increase its availability on a large scale. Alkaline water electrolysis is a mature and scalable technology, although it has several disadvantages compared to electrolyzers working in acidic environments. In particular, the use of highly alkaline aqueous electrolytes can lead to corrosion, and the achieved current densities are relatively low. This study addresses the latter limitation by introducing a gas diffusion electrode (GDE) setup as a novel development tool that bridges the gap between research and practical applications in commercial devices such as fuel cells and electrolyzers. A high surface area Ni foam catalyst that can sustain exceptional oxygen evolution reaction (OER) current densities of up to 4 A cm−2 in a quasi‐steady‐state within our GDE setup operating in an alkaline environment is presented. The high performance of this Ni‐based benchmark catalyst is attributed to its deposition onto a mesh‐like porous transport layer (PTL) via hydrogen‐templated electrodeposition. This forms a porous foam‐like structure that augments the mass transport of the gaseous reactants at the GDE.