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At least 217 records · Page 12

A pair of metal organic framework (MOF)-derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for zinc-air batteries

Metal organic frameworks (MOFs) are amazing precursors for the development of functional catalysts due to their ability of being modified both structurally and in terms of composition. Here this work presents a pair of MOF - derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for the advancement of zinc-air batteries. Zeolitic imidazolate frameworks (ZIF) are known as ideal materials to create doped carbons. Combining with a sacrificial tellurium template, we have developed a “pseudo-carbon nanotube” with a ZIF-8 that is doped with a mixture of zinc, cobalt, and iron. The resulting mixed-metal doped porous carbon nanotubes (CoFeZn@pCNT) show excellent catalytic activity for ORR with a half-way ORR potential (E 1/2 ) of 0.87 V vs. RHE (reverse hydrogen electrode). Iridium-based catalysts are known as the best option for OER so far, but it is not viable for practical applications due to cost restrictions. Previous research into alternative catalysts has focused on metal oxides with first-row transition metals. Metal sulfides provide superior conductivity compared to metal oxides and are a new frontier in the search for affordable, active, and stable OER catalysts. By combining cobalt, iron, and nickel into a MOF structure (ZIF-67), followed by a sulfurization process, a MOF-derived mixed-metal sulfide catalyst (FeCoNi–S@ZIF) has been developed in this study. The resulting catalysts show an onset OER potential of 1.65 V vs. RHE at 10 mA cm -2 and exhibit remarkable stability for the operation of zinc-air batteries.

25 ENERGY STORAGE↗

A general strategy for preparing pyrrolic-N 4 type single-atom catalysts via pre-located isolated atoms

Single-atom catalysts (SACs) have been applied in many fields due to their superior catalytic performance. Because of the unique properties of the single-atom-site, using the single atoms as catalysts to synthesize SACs is promising. In this work, we have successfully achieved Co 1 SAC using Pt 1 atoms as catalysts. More importantly, this synthesis strategy can be extended to achieve Fe and Ni SACs as well. X-ray absorption spectroscopy (XAS) results demonstrate that the achieved Fe, Co, and Ni SACs are in a M1-pyrrolic N 4 (M= Fe, Co, and Ni) structure. Density functional theory (DFT) studies show that the Co(Cp) 2 dissociation is enhanced by Pt 1 atoms, thus leading to the formation of Co 1 atoms instead of nanoparticles. These SACs are also evaluated under hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the nature of active sites under HER are unveiled by the operando XAS studies. These new findings extend the application fields of SACs to catalytic fabrication methodology, which is promising for the rational design of advanced SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxygen-Plasma-Induced Hetero-Interface NiFe2O4/NiMoO4 Catalyst for Enhanced Electrochemical Oxygen Evolution

The electrolysis of water to produce hydrogen is an effective method for solving the rapid consumption of fossil fuel resources and the problem of global warming. The key to its success is to design an oxygen evolution reaction (OER) electrocatalyst with efficient conversion and reliable stability. Interface engineering is one of the most effective approaches for adjusting local electronic configurations. Adding other metal elements is also an effective way to enrich active sites and improve catalytic activity. Herein, high-valence iron in a heterogeneous interface of NiFe 2 O 4 /NiMoO 4 composite was obtained through oxygen plasma to achieve excellent electrocatalytic activity and stability. In particular, 270 mV of overpotential is required to reach a current density of 50 mA cm -2 , and the overpotential required to reach 500 mA cm -2 is only 309 mV. The electron transfer effect for high-valence iron was determined by X-ray photoelectron spectroscopy (XPS). The fast and irreversible reconstruction and the true active species in the catalytic process were identified by in situ Raman, ex situ XPS, and ex situ transmission electron microscopy (TEM) measurements. This work provides a feasible design guideline to modify electronic structures, promote a metal to an active oxidation state, and thus develop an electrocatalyst with enhanced OER performance.

36 MATERIALS SCIENCE↗

Evaluating the effect of ionomer chemical composition in silver-ionomer catalyst inks toward the oxygen evolution reaction by half-cell measurements and water electrolysis

The effect of anion exchange ionomer (AEI) chemistry on the kinetics of the oxygen evolution reaction (OER) was systematically studied in both half-cell and single-cell electrolysis experiments. OER was studied in 1 M K 2 CO 3 at 50°C using an array of ionomer-silver catalyst inks deposited on Ni foam. Different ionomer modifications were investigated to optimize the OER performance. The AEI used in this work features a block copolymer backbone of polychloromethylstyrene-b-polycyclooctene-b-polychloromethylstyrene which was functionalized with either benzyltrimethylammonium (TMA) or benzylmethylpiperidinium (MPRD) quaternary ammonium cations. Here, using an MPRD quaternary ammonium cation shifted the rate determining step at high overpotentials, ultimately providing enhanced performance. Increasing the catalyst ink dilution was also found to substantially improve mass activity and catalyst utilization (increase from 35 to 88 A g –1 Ag), likely by reducing the ionomer thickness and decreasing transport resistances. In the final ionomer modification, the Ni foam substrate was leveraged to partially hydrogenate the polycyclooctene midblock to be polyethylene-like at the Ni interface. A significant increase in the electrochemical surface area (Cdl increased from 8.8 to 20.8 mF cm –2 ) and performance (by 47 mA cm –2 or 29 A g –1 Ag) was observed with the incorporation of polyethylene. Kinetic results from half-cell experiments were validated via single-cell anion exchange membrane electrolysis experiments, where the optimized electrode displayed enhanced performance in both 1 M K 2 CO 3 and DI H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Influence of Transitional Metal Dopants on Reducing Chlorine Evolution during the Electrolysis of Raw Seawater

Electrocatalytic water splitting is a possible route to the expanded generation of green hydrogen; however, a long-term challenge is the requirement of fresh water as an electrolyzer feed. The use of seawater as a direct feed for electrolytic hydrogen production would alleviate fresh water needs and potentially open an avenue for locally generated hydrogen from marine hydrokinetic or off-shore power sources. One environmental limitation to seawater electrolysis is the generation of chlorine as a competitive anodic reaction. This work evaluates transition metal (W, Co, Fe, Sn, and Ru) doping of Mn-Mo-based catalysts as a strategy to suppress chlorine evolution while sustaining catalytic efficiency. Electrochemical evaluations in neutral chloride solution and raw seawater showed the promise of a novel Mn-Mo-Ru electrode system for oxygen evolution efficiency and enhanced catalytic activity. Subsequent stability testing in a flowing raw seawater flume highlighted the need for improved catalyst stability for long-term applications of Mn-Mo-Ru catalysts. This work highlights that elements known to be selective toward chlorine evolution in simple oxide form (e.g., RuO2) may display different trends in selectivity when used as isolated dopants, where Ru suppressed chlorine evolution in Mn-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Acidic Oxygen Evolution Activity by Supporting Iridium Electrocatalysts on Tantalum Carbide

For a high-performance proton exchange membrane water electrolyzer (PEMWE), acidic oxygen evolution reaction (OER) electrocatalysts require highly dispersed iridium oxide (IrO x ) nanoparticles. Although carbon-based materials have been explored as promising supports for IrO x nanoparticles, their limited stability under harsh oxidative and acidic PEMWE conditions remains a significant challenge. Here, in this study, we report the synthesis and in situ characterization of active and durable IrOx electrocatalysts supported on electrochemically stable and electrically conducting tantalum carbide (TaC). When applied in a PEMWE, the IrO x /TaC electrocatalyst achieves a cell voltage of 1.71 V at 1.0 A cm –2 , outperforming the commercial IrO 2 catalyst (1.82 V at 1.0 A cm –2 ). Furthermore, the IrO x /TaC catalyst maintains a stable operation for 200 h at 0.5 A cm –2 with a low degradation rate of 36 μV h –1 . Density functional theory calculations further confirm that Ir–O–Ta bond formation at the IrO x /TaC interface reduces the overpotential of the OER compared to IrO 2 . This study underscores the pivotal role of supporting IrO x over stable and conducting metal carbides, providing guidance for the design of advanced acidic OER catalysts.

58 GEOSCIENCES↗

Periodic Porous 3D Electrodes Mitigate Gas Bubble Traffic during Alkaline Water Electrolysis at High Current Densities

We report alkaline water electrolysis at high current densities is plagued by gas bubble generation and trapping in stochastic porous electrodes (e.g., Ni foams), which causes a significant reduction in the number of electrolyte accessible catalyst active sites. Here, 3D printed Ni (3DPNi) electrodes with highly controlled, periodic structures are reported that suppress gas bubble coalescence, jamming, and trapping and, hence, result in rapid bubble release. The 3DPNi electrodes decorated with carbon-doped NiO achieve a high current density of 1000 mA cm -2 in 1.0 m KOH electrolyte at hydrogen evolution reaction and oxygen evolution reaction overpotentials of 245 and 425 mV, respectively. This work demonstrates a new approach to the deterministic design of 3D electrodes to facilitate rapid bubble transport and release to enhance the total electrode catalytic activity at commercially relevant current densities.

08 HYDROGEN↗

Catalytic Water Electrolysis by Co–Cu–W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co–Cu–W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co 2+ (octahedral), Cu + / 2+ (tetrahedral/square-planar), and W 6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co 3+ and Cu 0 are the active catalytic sites involved in the OER and HER, respectively, while Cu 2+ and W 6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co–Cu–W MMO system. In conclusion, these results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co 3+ hydroperoxide, whose formation is accompanied by changes in the Cu–O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Insights into the Electrochemical Oxidation of 5-Hydroxymethylfurfural on a Thin-Film Ni Anode

The electrochemical oxidation of alcohols is being explored as a favorable substitute for the oxygen evolution reaction owing to its capability to generate high-value products and lower overpotentials. Herein, we present a systematic investigation into the electrochemical oxidation of 5-hydroxymethylfurfural (HMF), a model biomass platform chemical, on a thin-film nickel catalyst, aiming to investigate the underlying reaction mechanism and shed light on the role of the catalyst’s microenvironment and phase on activity and product selectivity. Utilizing a combined experimental and computational approach, we demonstrate that NiOOH is the active phase for HMF oxidation. Additionally, we find a substantial impact of the electrochemical environment, particularly the electrolyte pH, on the reaction. Under highly alkaline conditions (pH = 13), higher activity for HMF oxidation is observed, accompanied by an increased selectivity toward 2,5-furandicarboxylic acid (FDCA) production. Conversely, a less alkaline environment (pH = 11) results in diminished HMF oxidation activity and a higher preference for the partial oxidation product 2,5-diformylfuran (DFF). Mechanistic insights from DFT studies reveal that geminal diols that are present under highly alkaline conditions undergo hydride transfer via HMFCA, while a shift to an alkoxide route occurs at a lower pH, favoring the DFF pathway. Hydride transfer energetics are also strongly affected by the surface Ni oxidation state. Finally, this integrated approach, bridging experimental and computational insights, provides a general framework for investigating the electrochemical oxidation of aldehydes and alcohols, thereby advancing rational design strategies in electrocatalysts for alcohol electro-oxidation reactions.

30 DIRECT ENERGY CONVERSION↗

Porous Two-dimensional Iron-Cyano Nanosheets for High-rate Electrochemical Nitrate Reduction

Ammonia (NH 3 ) is an essential ingredient in agriculture and a promising source of clean energy as a hydrogen carrier. The current major method for ammonia production, however, is the Haber–Bosch process that leads to massive energy consumption and severe environmental issues. Compared with nitrogen (N 2 ) reduction, electrochemical nitrate reduction reaction (NO 3 RR), with a higher NH 3 yield rate and Faradaic efficiency, holds promise for efficient NH 3 production under ambient conditions. To achieve efficient NO 3 RR, electrocatalysts should exhibit high selectivity and Faradaic efficiency with a high NH 3 yield rate. In this work, we developed two-dimensional (2D) iron-based cyano-coordination polymer nanosheets (Fe-cyano NSs) following in situ electrochemical treatment for high-rate NO 3 RR. Owing to the strong adsorption of nitrate on Fe0 active sites generated via topotactic conversion and in situ electroreduction, 2D Fe-cyano electrocatalyst exhibits high catalytic activity with a yield rate of 42.1 mg h –1 mgcat –1 and a Faradaic efficiency of over 90% toward NH 3 production at –0.5 V (vs reversible hydrogen electrode, RHE). Further electrochemical characterizations revealed that superhydrophilic surface and enhanced electrochemical surface area of the 2D porous nanostructures also contributed to the high-rate NO 3 RR activity. Finally, an electrolyzer toward NO 3 RR and oxygen evolution reaction (OER) in a two-electrode configuration is constructed based on 2D Fe-cyano, achieving an energy efficiency of 26.2%. This work provides an alternative methodology toward topotactic conversion of transition metal nanosheets for NO 3 RR and reveals the often-overlooked contribution of hydrophilicity of the catalysts for high-rate electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transformation of Highly Stable Pt Single Sites on Defect Engineered Ceria into Robust Pt Clusters for Vehicle Emission Control

Engineering surface defects on metal oxide supports could help promote the dispersion of active sites and catalytic performance of supported catalysts. Herein, a strategy of ZrO 2 doping was proposed to create rich surface defects on CeO 2 (CZO) and, with these defects, to improve Pt dispersion and enhance its affinity as single sites to the CZO support (Pt/CZO). The strongly anchored Pt single sites on CZO support were initially not efficient for catalytic oxidation of CO/C 3 H 6 . However, after a simple activation by H 2 reduction, the catalytic oxidation performance over Pt/CZO catalyst was significantly boosted and better than Pt/CeO 2 . Pt/CZO catalyst also exhibited much higher thermal stability. The structural evolution of Pt active sites by H 2 treatment was systematically investigated on aged Pt/CZO and Pt/CeO 2 catalysts. With H 2 reduction, ionic Pt single sites were transformed into active Pt clusters. Much smaller Pt clusters were created on CZO (ca. 1.2 nm) than on CeO 2 (ca. 1.8 nm) due to stronger Pt-CeO 2 interaction on aged Pt/CZO. Consequently, more exposed active Pt sites were obtained on the smaller clusters surrounded by more oxygen defects and Ce 3+ species, which directly translated to the higher catalytic oxidation performance of activated Pt/CZO catalyst in vehicle emission control applications.

36 MATERIALS SCIENCE↗

Electron Redistributed S-Doped Nickel Iron Phosphides Derived from One-Step Phosphatization of MOFs for Significantly Boosting Electrochemical Water Splitting

Nonprecious transition metal-organic frameworks (MOFs) are one of the most promising precursors for developing electrocatalysts with high porosity and structural rigidity. This study reports the synthesis of high efficiency electrocatalysts based on S-doped NiFeP. MOF-derived S-doped NiFeP structure is synthesized by a one-step phosphorization process with using S-doped MOFs as the precursor, which is more convenient and environment friendly, and also helps retain the samples’ framework. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance of the NiFeP catalysts can be improved after partially replacing P by S due to the tunable electronic structure. The optimized CCS-NiFeP-10 reaches a current density of 10 mA cm –2 for OER with an overpotential of 201 mV and outperforms most NiFe-based catalysts. The S doping plays an important role in tuning the ΔG values for intermediates formation in Ni atoms to a suitable value and exhibits a pronouncedly improved the OER performance. CCS-NiFeP-20 sample presents excellent HER performance due to the d-band center downshifting from the Fermi level. When the voltage of the electrolytic cell is 1.50 V, a current density of 10 mA cm –2 can be obtained. This strategy paves the way for designing highly active none-noble metal catalysts.

36 MATERIALS SCIENCE↗

Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?

Ni oxides and oxyhydroxides (NiO x ) have been studied for a long time as cathode materials for alkaline batteries and electrocatalysts for the oxygen evolution reaction (OER). Yet, understanding of the connection between their atomic and electronic structures and electrochemical performance or stability is still incomplete. In this work, we use first-principles density functional theory (DFT) calculations to revisit the structure, electronic properties, and OER activity of β-NiOOH, the catalytically active phase of NiO x . Following extensive DFTbased screening, we identify a hitherto overlooked structure characterized by a uniform distribution of H atoms on the NiO 2 layers. All the Ni 3+ cations in this structure exhibit an identical t g 6 e g 1 electronic configuration with an occupied 3d z2 orbital. Comparison of the calculated bond lengths with extended X-ray absorption fine structure (EXAFS) data unequivocally supports this structure relative to all other low-energy configurations. Based on this structure, we uncover and detail defect-dominated OER mechanisms on the basal β-NiOOH (001) surface, with overpotentials as low as 0.39 V. The present results should provide a valuable contribution to ongoing efforts for understanding and developing enhanced transition-metal hydroxide catalysts for the OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stone-Wales defect-rich carbon-supported dual-metal single atom sites for Zn-air batteries

In this study, we aim to obtain a fundamental understanding of active sites near stone-wales (SW) defects rich nitrogen-doped graphene (DG) with specific coordination of carbon atom rings. It reveals that the SW rich defects ( e.g., pentagon (5), pentagon—octagon—pentagon ( i.e . 585), or pentagon-heptagon-heptagon-pentagon (5775) rings, appears correspondingly with carbon rings that brought active sites during catalytic reactions. Moreover, we anchored dual isolated metallic atoms (Ni/Fe) on DG support via linkers (O/N) called NiFe-DG. X-ray absorption spectroscopy indicates Ni/Fe metal single atoms are embedded via Fe-N 4 and Ni-N 4 coordination on DG surfaces. It exhibits high catalytic activity for oxygen reduction reaction (ORR) with an onset potential of 0.97 V, a half-wave potential of 0.86 V, and diffusion current density of 5.7 mA cm – 2 , which is at par with commercial Pt/C. The catalyst shows superior stability, retained 82% of the initial current density even after 12 h under an applied potential of 0.86 V. Similarly, the oxygen evolution reaction (OER) overpotential of 358 mV was achieved at 10 mA cm – 2 with a lower Tafel slope value (76 mV/dec) than commercial Pt/C. It maintains 85% stability for 12 h at a constant potential of 1.588 V, shows better stability than commercial Pt/C.

25 ENERGY STORAGE↗

Morphology-driven oxygen evolution performance of NiO x nanostructures and implications for hole transport in perovskite solar cells

Morphology-controlled nanostructures provide an effective strategy to modulate both oxygen evolution reaction (OER) activity and photovoltaic performance in perovskite solar cells (PSCs). However, achieving low OER overpotentials and high power conversion efficiency (PCE) simultaneously through morphology engineering remains challenging. In this work, nickel oxide (NiO x ) nanostructures with spindle-like (NiO x -NS) and plate-like (NiO x -NP) morphologies were synthesized and evaluated as bi-functional OER catalysts and hole transport layers (HTLs) in inverted PSCs. Structural and thermal analyses reveal that NiO x -NS crystallizes into a cubic phase at a lower temperature (300 °C), whereas NiO x -NP requires higher calcination temperatures, reflecting differences in precursor microstructure. Electrochemical measurements indicate that NiO x -NS calcined at 300 °C delivers the lowest OER overpotential (395 mV at 10 mA cm −2 ), outperforming NiO x -NP calcined at 400 °C (565 mV) and 500 °C (474 mV). This enhanced activity is ascribed to favorable surface strain, increased defect density, and advantageous facet exposure. When used as HTLs, NiO x -NS also delivers the highest PCE (13.25%) among all tested devices, exceeding those based on NiO x -NP and commercial NiO x , owing to improved hole extraction and interfacial contact. Overall, this study highlights the importance of morphology control and thermal processing in tailoring NiO x for multifunctional nanomaterials in electrocatalytic and photovoltaic applications.

36 MATERIALS SCIENCE↗

Six-coordinate ruthenium water oxidation catalysts bearing equatorial polypyridinedicarboxylato and axial phosphine ligands

Ruthenium catalysts for water oxidation combining multidentate ligands [2,2':6',2"-terpyridine]-6,6"-dicarboxylato (tda) and 2,2'-bipyridine-6,6'-dicarboxylato (bda) with apical phosphine ligands have been prepared. Here, these new complexes were fully characterized by standard spectroscopic and single-crystal X-ray crystallography analyses, and their redox properties were evaluated by electrochemistry. Specifically, [Ru II (tda)(tris(2-furyl)phosphine) 2 ] displayed two reversible redox waves that were assigned to the Ru II/III and Ru III/IV transitions, respectively. The number of turnovers in Ce IV -driven water oxidation reached 258 for the bda analog, and for the tda analog, early reaction rates were first order in initial catalyst concentration. The effects of adding fractional equivalents of Ce IV were studied using UV–vis spectroscopy. Steric and electronic changes in the axial phosphine ligand can exert their effects on the properties and catalytic activity of the resulting complexes, which may be useful when exploring other chemistry of these complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

N‐Doping Effects On Electrocatalytic Water Splitting of Non‐Noble High‐Entropy Alloy Nanoparticles Prepared by Inert Gas Condensation

Abstract The unique catalytic activities of high‐entropy alloys (HEAs) emerge from the complex interaction among different elements in a single‐phase solid solution. As a “green” nanofabrication technique, inert gas condensation (IGC) combined with laser source opens up a highly efficient avenue to develop HEA nanoparticles (NPs) for catalysis and energy storage. In this work, the novel N‐doped non‐noble HEA NPs are designed and successfully prepared by IGC. The N‐doping effects of HEA NPs on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are systematically investigated. The results show that N‐doping is conducive to improving the OER, but unfavorable for HER activity. The FeCoNiCrN NPs achieve an overpotential of 269.7 mV for OER at a current density of 10 mA cm −2 in 1.0 M KOH solution, which is among the best reported values for non‐noble HEA catalysts. The effects of the differences in electronegativity, ionization energy and electron affinity energy among mixed elements in N‐doped HEAs are discussed as inducing electron transfer efficiency. Combined with X‐ray photoelectron spectroscopy and the extended X‐ray absorption fine structure analysis, an element‐design strategy in N‐doped HEAs electrocatalysts is proposed to improve the intrinsic activity and ameliorate water splitting performance.

Chemistry↗