Electrocatalyst For Oxidation Research Articles

Impact of Fe2(MoO4)3 and ZnMoO4 on CO Tolerance of Pt/C catalysts for enhanced methanol electrooxidation efficiency

Success of Pt/C catalyst in electrooxidation of methanol is highly influenced by its ability to withstand the poisoning effects of carbonaceous species adsorbed on the catalytic surface. Covalently bonded CO molecules occlude the active sites of the catalytic surface, impeding methanol adsorption. In this study, Pt/C-based nanocomposite catalysts were synthesized incorporating Fe2(MoO4)3 and ZnMoO4 to form heterojunctions through intermittent microwave-assisted polyol method to augment the CO oxidation pathway by introducing hydroxy groups adsorbed on their surfaces. Thorough characterization of the catalysts elucidated their chemical and phase purity, bonding configurations, and oxidation states, with various electroanalytical techniques employed to probe the mechanism of activity enhancement. Furthermore, the distinctive electron density profiles of these molybdate species have been identified as potential facilitators of methanol adsorption on the platinum surface. Equimolar composition in formulating the composite catalysts yielded a fivefold increase in catalytic activity (with ZnMoO4) and a 1.5-fold increase (with Fe2(MoO4)3). This approach demonstrates promise for tailoring Pt/C catalysts to develop industrially viable CO-tolerant and highly stable electrocatalysts.

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 291 mV 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 were confirmed in long-term studies using an AEM electrolyzer.

Transfer learning guided discovery of efficient perovskite oxide for alkaline water oxidation

Perovskite oxides show promise for the oxygen evolution reaction. However, numerical chemical compositions remain unexplored due to inefficient trial-and-error methods for material discovery. Here, we develop a transfer learning paradigm incorporating a pre-trained model, ensemble learning, and active learning, enabling the prediction of undiscovered perovskite oxides with enhanced generalizability for this reaction. Screening 16,050 compositions leads to the identification and synthesis of 36 new perovskite oxides, including 13 pure perovskite structures. Pr0.1Sr0.9Co0.5Fe0.5O3 and Pr0.1Sr0.9Co0.5Fe0.3Mn0.2O3 exhibit low overpotentials of 327 mV and 315 mV at 10 mA cm−2, respectively. Electrochemical measurements reveal coexistence of absorbate evolution and lattice oxygen mechanisms for O-O coupling in both materials. Pr0.1Sr0.9Co0.5Fe0.3Mn0.2O3 demonstrates enhanced OH- affinity compared to Pr0.1Sr0.9Co0.5Fe0.5O3, with the emergence of oxo-bridged Mn-Co conjugate facilitating charge redistribution and dynamic reversibility of Olattice/VO, thereby slowing down Co dissolution. This work paves the way for accelerated discovery and development of high-performance perovskite oxide electrocatalysts for this reaction.

Manganese-Mediated Electrochemical Oxidation of Thioethers to Sulfoxides Using Water as the Source of Oxygen Atoms.

Oxygen-atom transfer reactions are a prominent class of synthetic redox reactions that often use high-energy oxygen-atom donor reagents. Electrochemical methods can bypass these reagents by using water as the source of oxygen atoms through pathways involving direct or indirect (mediated) electrolysis. Here, manganese porphyrins and related mediators are shown to be effective molecular electrocatalysts for selective oxidation of thioethers to sulfoxides, without overoxidation to the sulfone. The reactions proceed by proton-coupled oxidation of a MnIII-OH2 species to generate a MnIV-OH and MnV═O species. This methodology is compared to direct electrolysis methods initiated by single-electron oxidation of the thioether, and chloride-mediated electrochemical oxidation of thioethers. The Mn-mediated reactions operate at lower applied potential and exhibit improved substrate scope and functional group compatibility relative to direct electrolysis, and the tunability of the Mn-based mediators allows for improved performance relative to chloride-mediated electrolysis. An electrochemical parallel screening platform is developed and applied to a library of pharmaceutically relevant thioethers.

Self-Assembly of a Hierarchical Metal-Organic Framework at the Liquid/Liquid Interface via π-π Stacking Manipulations in Organoplatinum(IV) Complexes for Methanol Fuel Cells.

This study focuses on the facile synthesis of the hierarchical architecture of zeolitic imidazolate framework-8 (ZIF-8) films containing an ultrasmall amount of Pt(0) by investigating the synthesis of different organoplatinum complexes and manipulating the π-π stacking effect in these complexes at the liquid/liquid interface. The organometallic Pt(IV) precursors were complexes with a formula of [PtXMe2(R)(bpy)] (bpy = 2,2'-bipyridine; for complex 2, R = CH2CH═CHC6H5 and X = Br; for complex 3, R = CH2CH═CH2 and X = Br; for complex 4, R = Me and X = I) prepared by oxidative addition of cinnamyl bromide, allyl bromide, or methyl iodide to [PtMe2(bpy)] (complex 1). Different thin films were synthesized starting from three organometallic Pt(IV) precursors (i) by reduction of the Pt complexes at the toluene/water interface (TF2-TF4), (ii) by encapsulation of the Pt precursors in a ZIF-8 (TF5-TF7), and (iii) by reduction of the Pt precursors onto a ZIF-8 (TF8-TF10). The self-assembly of ZIF-8 and different organoplatinum precursors at the interface of two immiscible liquids leads to the preparation of films with well-engineered structures such as rhombic dodecahedra, nanorods, hierarchical architectures, and nanowires, which are very difficult and complicated to synthesize under normal conditions. The ultralow loading of platinum complexes with different degrees of π-π stacking of dangling moieties has a great impact on the structure and morphology (directing agent), which in turn drastically changes the catalytic properties. The obtained films were applied as electrocatalysts for methanol oxidation in fuel cells. The electrocatalytic performance of organoplatinum containing a cinnamyl group in hierarchical architecture TF8 was found to be superior to those of nonhierarchical structures.

Pd nanoparticles supported on silver, zinc, and reduced graphene oxide as a highly active electrocatalyst for ethanol oxidation

In this manuscript, we present a facile approach to synthesize a highly active catalyst for the electro-oxidation of ethanol using Pd nanoparticles supported on a Ag–Zn alloy on reduced graphene oxide. This nanocomposite material was fabricated via a two-step process of incineration followed by sol-gel synthesis. The physical properties of the catalyst were evaluated using X-ray diffraction, X-ray photoelectron spectroscopy, and scanning and transmission electron microscopies. To understand the catalyst's activity for ethanol oxidation, we performed a series of cyclic voltammetry and electrochemical impedance spectroscopy experiments in alkaline medium. The catalyst exhibited good catalytic activity with a current density of 13.01 mA cm−2, a value seven times higher than the commercial standard Pd/C catalyst and higher than any other previously reported Pd-based catalyst. The results were attributed synergistic effects between the Pd and alloy support along with the large electrochemically active surface area of the material. Taken together, these results suggest that ethanol electrocatalysts based on nanocomposites of Pd, Ag, and Zn is promising candidates for future ethanol fuel cells.

Component leaching of water oxidation electrocatalysts

AbstractMost electrocatalysts are known to experience structural change during the oxygen evolution reaction (OER) process. Considerable endeavors have been dedicated thus far to comprehending the catalytic process and uncovering the underlying mechanism. During the dynamic evolution of catalyst structure, component leaching of electrocatalysts is the most common phenomenon. This article offers a concise overview of recent findings and developments related to the leaching phenomena in the OER process in terms of fundamental understanding of leaching, advanced characterization techniques used to investigate leaching, leaching of inactive components, and leaching of active components. Leaching behaviors and the induced effects in various kinds of OER catalysts are discussed, progress in manipulating leaching amount/degree toward a tunable surface evolution is spotlighted, and finally, three representative types of structure transformations induced by leaching metastable species in OER condition are proposed. By understanding the process of component leaching in the OER, it will provide more guidance for the rational design of superior electrocatalysts.image

One-step hydrothermal preparation of CeMo-codoped Ni3S2 as robust bifunctional electrocatalyst for urea oxidation and methanol oxidation

The production of hydrogen via electrolytic water splitting is mainly limited by the high overpotential of the oxygen evolution reaction (OER). Thus, the replacement of OER with more thermodynamically favorable urea oxidation (UOR) and methanol oxidation (MOR) reactions shows good promise. In this paper, a CeMo-Ni3S2/NF bifunctional electrocatalyst for UOR and MOR electrolysis was prepared by a one-step hydrothermal method. The experiments reveal that the doped Ce and Mo cations significant modulate the morphology of Ni3S2, and thus significant boost the electrochemically active surface area and increase the UOR and MOR performance. At a current density of 100 mA cm−2, UOR requires a potential of 1.35 V (vs. RHE) and MOR requires 1.38 V (vs. RHE), which are both significantly lower than the potential of 1.59 V (vs. RHE) required for OER. The UOR reaction produces NO2- with a Faradaic efficiency of 69.0 %, while the MOR reaction produces formate with a Faradaic efficiency of 81.5 %. These results provide strategies for the development of advanced MOR and UOR electrode materials.

Nickel-modified poly(aniline-co-pyrrole) as electrocatalyst for electrochemical oxidation of methanol in direct methanol fuel cell application

Nickel-modified poly(aniline-co-pyrrole) as electrocatalyst for electrochemical oxidation of methanol in direct methanol fuel cell application

Rationally Designed L12-Pt2RhFe Intermetallic Catalyst with High CO-Tolerance for Alkaline Methanol Electrooxidation.

It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L12-Pt2RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt2RhFe/C achieves a superior mass activity of 6.43 A mgPt -1, which is 2.23-fold and 3.53-fold higher than those of PtRu/C and Pt/C. Impressively, the Pt2RhFe/C exhibits a significant enhancement in durability owing to its high CO-tolerance and stability. Density functional theory calculations reveal that high performance of Pt2RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt-CO···OH-Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.

Lithium cation-doped tungsten oxide as a bidirectional nanocatalyst for lithium-sulfur batteries with high areal capacity

Lithium-sulfur (Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide (Li2S) oxidation barrier, especially under high sulfur loadings. Here, we report a Li cation-doped tungsten oxide (LixWOx) electrocatalyst that efficiently accelerates the S↔Li2S interconversion kinetics. The incorporation of Li dopants into WOx cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li2S oxidation, along with enhanced Li+ diffusion. In conjunction with theoretical calculations, it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the LixWOx, which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics. Consequently, Li-S cells with the LixWOx bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings. Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.

Research on carbon black and cerium co-doped Ti4O7-CB-Ce electrocatalytic oxidation of tetracycline-based antibiotics.

Elemental doping is a promising way for enhancing the electrocatalytic activity of metal oxides. Herein, we fabricate Ti/ Ti4O7-CB-Ce anode materials by the modification means of carbon black and cerium co-doped Ti4O7, and this shift effectively improves the interfacial charge transfer rate of Ti4O7 and •OH yield in the electrocatalytic process. Remarkably, the Ti4O7-CB-Ce anode exhibits excellent efficiency of minocycline (MNC) wastewater treatment (100% removal within 20 min), and the removal rate reduces from 100 to 98.5% after five cycles, which is comparable to BDD electrode. •OH and 1O2 are identified as the active species in the reaction. Meanwhile, it is discovered that Ti/ Ti4O7-CB-Ce anodes can effectively improve the biochemical properties of the non-biodegradable pharmaceutical wastewater (B/C values from 0.25 to 0.44) and significantly reduce the toxicity of the wastewater (luminescent bacteria inhibition rate from 100 to 26.6%). This work paves an effective strategy for designing superior metal oxides electrocatalysts.

Nickel-based metal-organic-frameworks as electrocatalysts for electrochemical oxidation of ammonia

Electrochemical oxidation of ammonia can produce hydrogen by splitting the ammonia molecules, not merely facilitating the elimination of ammonia but also augmenting sustainable hydrogen-based technological systems. However, the anode reaction is sluggish and the development of novel electrocatalysts is the major method to overcome this demerit. Herein, three kinds of Ni-based MOFs (Ni-BDC, Ni-BTC, and Ni-NH2-BDC) were prepared and used as electrocatalysts towards electrochemical oxidation of ammonia for the first time. At optimized working condition (0.5 V), Ni-NH2-BDC presents the response current density of 2.12 mA/cm2 with the current efficiency of 92.6%, both of which are significantly higher than those of Ni-BDC and Ni-BTC, indicating the better performance of Ni-NH2-BDC. EIS tests and the measurement of conductivity revealed that the good performance of Ni-NH2-BDC could be attributed to the lower charge transfer resistance at the electrode/electrolyte interface and the significantly improved conductivity which is caused by the introduction of NH2 groups.This work shed lights on the development of MOFs electrocatalysts for ammonia oxidation as well as other electrochemical reactions.

Dynamic in situ reconstruction of NiSe2 promoted by interfacial Ce2(CO3)2O for enhanced water oxidation

Understanding and manipulating the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity. Herein, we present a synthesis of NiSe2-Ce2(CO3)2O heterostructure and demonstrate the efficacy of interfacial Ce2(CO3)2O in promoting the formation of catalytically active centers to improve oxygen evolution activity. In-situ Raman spectroscopy shows that incorporation of Ce2(CO3)2O into NiSe2 causes a cathodic shift of the Ni2+→Ni3+ transition potential. Operando electrochemical impedance spectroscopy reveals that strong electronic coupling at heterogeneous interface accelerates charge transfer process. Furthermore, density functional theory calculations suggest that actual catalytic active species of NiOOH transformed from NiSe2, which is coupled with Ce2(CO3)2O, can optimize electronic structure and decrease the free energy barriers toward fast oxygen evolution reaction (OER) kinetics. Consequently, the resultant NiSe2-Ce2(CO3)2O electrode exhibits remarkable electrocatalytic performance with low overpotentials (268/304 mV @ 50/100 mA cm−2) and excellent stability (50 mA cm−2 for 120 h) in the alkaline electrolyte. This work emphasizes the significance of modulating the dynamic changes in developing efficient electrocatalyst.

Pumpkin shell-derived activated carbon-supported S-incorporated transition metal oxide electrocatalyst for hydrogen evolution reaction

In the pursuit of a more sustainable future and to combat the environmental impact of fossil fuels, green hydrogen production through water electrolysis is gaining traction. While noble metals currently dominate electrocatalyst design, their expense limits widespread adoption. This study proposes a solution by outlining a method for designing efficient and affordable electrocatalysts based on non-precious metals. Herein, we introduce a novel S-incorporated Ni2O3 supported on biowaste-derived activated carbon (S-Ni2O3@AC) synthesized from pumpkin shells. This facile and sustainable approach utilizes readily available resources. The S-Ni2O3@AC nanocomposite demonstrates excellent HER performance with low overpotential and high durability. This is attributed to a high surface area of the composite, fast charge transfer, optimal hydrogen adsorption, and lowered energy barrier for water dissociation facilitated by sulfur incorporation, which is demonstrated by density functional theory (DFT) calculations. This research paves the way for cost-effective and sustainable hydrogen evolution electrocatalysts.

Interconnected Pd Nanowire Networks Stereoassembled on Biomass-Derived Porous Carbon Skeletons as Bifunctional Electrocatalysts for Efficient Methanol and Formic Acid Oxidation

Interconnected Pd Nanowire Networks Stereoassembled on Biomass-Derived Porous Carbon Skeletons as Bifunctional Electrocatalysts for Efficient Methanol and Formic Acid Oxidation

Unveiling the kinetics of oxygen evolution reaction in defect-engineered B/P-incorporated cobalt-oxide electrocatalysts

Defect-rich transition-metal oxide electrocatalysts hold great promise for alkaline water electrolysis due to their enhanced activity and stability. This study presents a new strategy that significantly improve the OER activity of Co-oxide nanosheets through incorporation of B and P (B/P-CoOx NS), eventually leading to abundant surface defects and oxygen vacancies. The B/P-CoOx NS demonstrates low overpotential of 220 mV to achieve 10 mA/cm2. The electrochemical and kinetic studies coupled with conventional morphological and structural characterizations, reveal that various crystalline defects like vacancies, dislocations, twin planes, and grain boundaries play crucial roles in promoting the OH− ion adsorption, the formation of intermediates, and the desorption of oxygen molecules. The industrial viability of the developed electrocatalyst is substantiated through assessments under harsh industrial conditions of 6 M KOH at 60 °C in a zero-gap single-cell alkaline electrolyzer which achieves 1 A/cm2 at 1.95 V. Chronoamperometry tests (100 h) highlight remarkable robustness of the electrocatalyst. This work establishes a new strategy to fabricate defect-rich OER electrocatalysts, setting a precedent to achieve better OER rates with non-noble materials.

Three‐Dimensionally Arranged NiSe2 Nanosheets as an Efficient Electrocatalyst for Methanol Electrooxidation Reaction

Methanol oxidation stands out as a pivotal solution in addressing the global energy crisis and environmental pollution, owing to its practical applicability, high current density, and the ready availability of methanol as a fuel source. To effectively catalyze methanol oxidation, an electrocatalyst is imperious to overcome the activation energy barrier. Herein, a three‐dimensionally arranged NiSe2 nanosheet‐based electrocatalyst is synthesized through a facile solvothermal followed by an annealing method. The catalyst's porous structure enhances catalytic efficiency by providing a substantial electrochemical surface area (ECSA) equivalent to 0.121 mF cm−2. Notably, the electrocatalyst exhibits a remarkable response of 21.58 mA cm−2 at an overpotential of 1.70 V vs RHE, accompanied by the lowest Tafel slope recorded at 39.14 mV dec−1. The electronic circuit, represented by Rs(Qf(RfW(QdlRct)), aligns well with electrochemical impedance spectroscopy data, elucidating the reaction path and intrinsic properties. Furthermore, the catalytic performance is elucidated concerning ECSA and weight, revealing current densities of 5.60 mA cm−2 and 71.34 mA mg−1, respectively. Impressively, the catalyst demonstrates exceptional resistance to poisoning and sustained stability over a continuous 3600‐s operation. This comprehensive study underscores the promising potential of the NiSe2 nanosheet‐based electrocatalyst for efficient methanol oxidation, providing valuable insights for advancing clean energy technologies.

Open Active Sites in Ni-Based MOF with High Oxidation States for Electrooxidation of Benzyl Alcohol.

The kinetics of electrocatalytic reactions are closely related to the number and intrinsic activity of the active sites. Open active sites offer easy access to the substrate and allow for efficient desorption and diffusion of reaction products without significant hindrance. Metal-organic frameworks (MOFs) with open active sites show great potential in this context. To increase the density of active sites, trimesic acid was utilized as a ligand to anchor more Ni sites and in situ construct the nickel foam-loaded Ni-based trimesic MOF electrocatalyst (Ni-TMA-MOF/NF). When tested as an electrocatalyst for benzyl alcohol oxidation, Ni-TMA-MOF/NF exhibited lower overpotential and superior durability compared to Ni foam-loaded Ni-based terephthalic MOF electrocatalyst (Ni-PTA-MOF/NF) and Ni(OH)2 nanosheet array (Ni(OH)2/NF). Ni-TMA-MOF/NF required only a low potential of 1.65 V to achieve a high current density of 400 mA cm-2. Even after 40000 s of electrocatalytic oxidation at 1.5 V, Ni-TMA-MOF/NF maintained a current density of 175 mA cm-2 with ∼68% retention, showing its potential for benzyl alcohol oxidation. Through a combination of experimental and theoretical investigations, it was found that Ni-TMA-MOF/NF displayed superior electrocatalytic activity due to an optimized electron structure with high-valence Ni species and a high density of active sites, enabling long-term stable operation at high current densities. This study provides a new perspective on the design of electrocatalysts for benzyl alcohol oxidation.

Enthralling Anodic Protection by Molybdate on High-Entropy Alloy-Based Electrocatalyst for Sustainable Seawater Oxidation.

Efficient and sustainable seawater electrolysis is still limited due to the interference of chloride corrosion at the anode. The designing of suitable electrocatalysts is one of the crucial ways to boost electrocatalytic activity. However, the approach may fall short as achieving high current density often occurs in chlorine evolution reaction (CER)-dominating potential regions. Thereby, apart from developing an OER-active high-entropy alloy-based electrocatalyst, the present study also offers a unique way to protect anode surface under high current density or potential by using MoO4 2- as an effective inhibitor during seawater oxidation. The wide variation of d-band center of high-entropy alloy-based electrocatalyst allows great oxygen evolution reaction (OER) proficiency exhibiting an overpotential of 230mV at current density of 20mA cm-2. Besides, the electrocatalyst demonstrates impressive stability over 500h at high current density of 1 A cm-2 or at a high oxidation potential of 2.0V versus RHE in the presence of a molybdate inhibitor. Theoretical and experimental studies reveal MoO4 2- electrostatically accumulated at anode surface due to higher adsorption ability, thereby creating a protective layer against chlorides without affecting OER.