Ethanol Oxidation Reaction Research Articles

Incorporation of Bimetallic Nanoparticles in Zeolitic Imidazolate Framework‐67 (ZIF‐67) for Use as a Catalyst for Ethanol Oxidation

AbstractRecently, direct ethanol fuel cells (DEFCs) have been attaining a crucial role in energy resources and transportable devices. Many of the researchers in DEFCs has begin to engage considerable focus due to their high electrocatalytic activity, enormous stability, portability, and inexpensive. In this study, we present an anchoring of bimetallic Pd‐Cu nanoparticles supported ZIF‐67 catalyst (Pd‐Cu@ZIF‐67) for high‐performance electro‐oxidation of ethanol for direct alcohol fuel cells (DAFCs) applications. Structural, morphological, and elemental composition of the proposed catalyst were examined by using UV–vis spectroscopy, XRD, FE‐SEM, and EDX. Further, the electrochemical properties of Pd‐Cu@ZIF‐67 catalyst for ethanol oxidation in basic media were explored by using various electrochemical techniques. According to the results, the suggested catalyst showed maximum ECSA (128.7 m2g−1), higher current density (894.06 mA cm−2), durability (750s), and improved long‐term stability (230 cycles) than the other controlled catalysts towards ethanol oxidation reaction. This enhanced of the Pd‐Cu@ZIF‐67 catalyst is to the synergistic effects of Pd‐Cu nanoparticles and outstanding support material (ZIF‐67). These findings highly suggest the Pd‐Cu@ZIF‐67 catalyst as an anodic potential material in fuel cell applications.

High-Entropy PdRhFeCoMo Metallene With High C1 Selectivity and Anti-Poisoning Ability for Ethanol Electrooxidation.

The urgent demand for designing highly efficient electrocatalysts for ethanol oxidation reaction (EOR) with elevated C1 selectivity, robust anti-poisoning capability, and high mass activity presents a formidable challenge. Herein, a novel two-dimentional (2D) high-entropy PdRhFeCoMo metallene (PdRhFeCoMo HEM) electrocatalyst is successfully synthesized via a mild one-step solvothermal method. The PdRhFeCoMo HEM, characterized by intentionally designed multi-metallic ensembles and ultra-thin graphene-like structures, delivers an impressive mass activity of 7.47 A mgPd+Rh -1 and specific activity of 25.5mA cm-2. Furthermore, it can retain a mass activity of 0.56 A mgPd+Rh -1 after undergoing 20000 s of continuous testing, demonstrating outstanding resistance to poisoning. More significantly, the PdRhFeCoMo HEM demonstrates an elevated capacity for C─C bond cleavage with a superior C1 selectivity of up to 84.12%. In situ spectroscopy analysis, combined with theoretical calculations, reveals that the deliberate design of components and structures effectively regulate the electronic properties of the Pd site, thereby enhancing the adsorption of reactant and reducing the reaction barrier of the C1 pathway. Finally, a flexible solid-state ethanol fuel cell assembled by PdRhFeCoMo HEM presents a maximum power density of 20.1mW cm-2 and can operate continuously by repeatedly adding ethanol fuel.

A Carbon-Particle-Supported Palladium-Based Cobalt Composite Electrocatalyst for Ethanol Oxidation Reaction (EOR)

For the first time, carbon-particle-supported palladium-based cobalt composite electrocatalysts (abbreviated as PdxCoy/CPs) were prepared using a calcination–hydrothermal process–hydrothermal process (denoted as CHH). The catalysts of PdxCoy/CPs prepared using CoC2O4·2H2O, (CH3COO)2Co·4H2O, and metallic cobalt were named catalyst c1, c2, and c3, respectively. For comparison, the catalyst prepared in the absence of a Co source (denoted as Pd/CP) was identified as catalyst c0. All fabricated catalysts were thoroughly characterized by XRD, EDS, XPS, and FTIR, indicating that PdO, metallic Pd, carbon particles, and a very small amount of cobalt oxide were the main components of all produced catalysts. As demonstrated by the traditional electrochemical techniques of CV and CA, the electrocatalytic performances of PdxCoy/CP towards the ethanol oxidation reaction (EOR) were significantly superior to that of Pd/CP. In particular, c1 showed an unexpected electrocatalytic activity for EOR; for instance, in the CV test, the peak f current density of EOR on catalyst c1 was 129.3 mA cm−2, being about 10.7 times larger than that measured on Pd/CP, and in the CA test, the polarized current density of EOR recorded for c1 after 7200 s was still about 2.1 mA cm−2, which was larger than that recorded for Pd/CP (0.6 mA cm−2). In the catalyst preparation process, except for the elements of C, O, Co, and Pd, no other elements were involved, which was thought to be the main contribution of this preliminary work, being very meaningful to the further exploration of Pd-based composite EOR catalysts.

A Nitrogen- and Carbon-Present Tin Dioxide-Supported Palladium Composite Catalyst (Pd/N-C-SnO2)

For the first time, nitrogen- and carbon-present tin dioxide-supported palladium composite catalysts (denoted as Pd/N-C-SnO2) were prepared via an HCH method (HCH is the abbreviation for the hydrothermal process–calcination–hydrothermal process preparation process). In this work, firstly, three catalyst carriers (denoted as cc) were prepared using a hydrothermal-process-aided calcination method, and catalyst carriers prepared using ammonia monohydrate (NH3∙H2O), N,N-dimethylformamide (C3H7NO) and triethanolamine (C6H15NO3) as the nitrogen sources were nominated as cc1, cc2 and cc3, respectively. Secondly, these catalyst carriers were reacted with palladium oxide monohydrate (PdO·H2O) hydrothermally to generate catalysts c1, c2 and c3. As testified by XRD and XPS, besides carbon materials and the N-containing substances, the main substances of all prepared catalysts were SnO2 and metallic palladium (Pd). Above all things, all resultant catalysts, especially c2, showed a prominent electrocatalytic activity towards the ethanol oxidation reaction (EOR). As indicated by the CV (cyclic voltammetry) results, all fabricated catalysts presented a clear electrocatalytic activity towards the EOR. In the CA (chronoamperometry) measurement, the faradaic current density of EOR measured on c2 at −0.27 V vs. an SCE (saturated calomel electrode) after 7200 s was still maintained at about 5.6 mA cm−2. Preparing a novel catalyst carrier, N-C-SnO2, and preparing a new EOR catalyst, Pd/N-C-SnO2, were the principal dedications of this preliminary work, which was very beneficial to the development of Pd-based EOR catalysts.

Platinum and CeO2−x Occlusion Electrodeposition at Unsupported Vulcan XC-72R for Methanol and Ethanol Oxidation Reactions in Alkaline Media

Platinum was electrodeposited in a slurry solution of CeO2 and Vulcan XC-72R to produce Pt/CeO2−x/Vulcan XC-72R catalysts by using the Rotating Disk Slurry Electrodeposition (RoDSE) Technique. The activity of the catalysts was measured towards methanol and ethanol oxidation reactions in alkaline conditions by cyclic voltammetry and chronoamperometry. The electrochemical results were compared to those obtained on commercial catalysts. Pt/CeO2−x/Vulcan XC-72R (with ∼ 26 wt% Pt) catalyst was the most active for both alcohol oxidation reactions when compared to commercial 40 wt.% and 20% /Vulcan XC-72R (ETEK) catalysts. The mass activity increases 2.0x and 2.4x for methanol and ethanol oxidation reactions when compare with 40 and 20 Pt wt. % commercial catalysts, respectively. The Pt/CeO2−x/Vulcan XC-72R catalysts contained Pt nanoparticles growth within the cerium oxide through an occlusion electrodeposition method. These effects were systematically investigated using X-ray Diffraction (XRD), High Resolution Transmission Electron Microscopy (HR-TEM), and X-ray Photoelectron Spectroscopy (XPS).

Molybdenum-doping to enhance the deprotonation ability of nickel-based hydroxide electrocatalysts for ethanol oxidation

With technological advancements, the practical application of ethanol oxidation reaction (EOR) is becoming increasingly promising, yet the need for higher ethanol concentrations highlights the growing importance of the deprotonation ability (Ni2+ to Ni3+) of the catalyst. The deprotonation ability is the key step for nickel-based catalysts in EOR, as it is essential for Ni2+ to continuously undergo deprotonation to transform into Ni3+ in order to maintain the continuous EOR. Herein, we developed Mo-doped Ni(OH)2 nanosheets by a hydrothermal method. The Mo-doped Ni(OH)2 nanosheets show excellent EOR performance due to the high valence doping of Mo, the onset potential of the oxidation peak (Ni2+ to Ni3+) appears at a position with a small overpotential,. The in-situ Raman spectroscopy technique further characterized the increase in NiOOH in the process of EOR. The Mo-doped Ni(OH)2 nanocomposite catalyst facilitates the oxidation of Ni2+ into Ni3+. Based on the above theoretical guidance, Mo-doped Fe/Ni(OH)2 nanosheets was designed and synthesized. The outstanding EOR performance of the Mo-Fe/Ni(OH)2-3 showed a potential of 1.352 V at 10 mA cm−2. The catalyst was used to design three-electrode reversible zinc-ethanol-air battery (T-RZEAB), which effectively overcomes the opposing kinetic and thermodynamic requirements for EOR and oxygen reduction reaction (ORR) catalysts in the oxygen electrode. The charging voltage of T-RZEAB with Mo-Fe/Ni(OH)2-3 is 240 mV lower than that of a traditional zinc-air battery at 25 mA cm−2.

The Effect of Saccharin on SnNi Alloy: the Electrodeposition and its Electrocatalytic Activity in Ethanol Oxidation Reaction

The development of Direct Ethanol Fuel Cell (DEFC) has attracted much attention, as alternative energy sources due to its various advantages. However, among its various advantages, DEFC has several problems, such as the kinetics of the ethanol oxidation reaction. Transition metal-based catalysts such as nickel and tin are considered as potential catalysts for DEFC due to their oxophilic properties that can improve catalytic activity. In this study, the effect of saccharin on SnNi bimetallic alloy catalyst synthesized by electrodeposition method on copper wire substrate was investigated. SnNi samples were characterized by several techniques, including X-ray diffraction, Scanning electron microscopy, and energi dispersive X-ray spectrocopy. Saccharin addition had a significant effect on the morphology, crystallite size, and composition of the catalyst. The presence of saccharin causes the formation of more uniform particles and has a smaller size. The sample with the addition of saccharin had a smaller charge transfer resistance value 4.82 Ω, lower tafel slope by 115 mV/dec, and show higher jf/jb ratio by 0.55. Furthermore, as the current density decreases, the SnNi catalyst with saccharin has a slow decrease rate and higher stability than the SnNi catalyst without saccharin.

Promoting role of Europium on Multi-Walled Carbon Nanotube (MWCNT) supported Platinum catalyst for Ethanol Electro-Oxidation in Direct Alcohol Fuel Cell (DAFC)

Implementing rare earth metals with platinum for Ethanol Oxidation Reactions (EOR) has received significant interest in the promising DEFC. Incorporation of Europium, a rare earth metal, influences the electron density of the Pt, and the resulting catalytic activity is reinforced. Herein, different molar ratios of binary PtEu electrocatalysts supported over MWCNT were synthesized using the borohydride reduction method. The purpose of the investigation was to determine how the atomic structure, composition, and activity of the electrocatalyst correlate to the EOR. Structure, bulk composition, morphology, and bonding of the electrocatalyst were investigated through X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray (EDX), Fourier Transform Infrared (FTIR) spectroscopy, and RAMAN spectroscopy. Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), chronoamperometry (CA), and Electrochemical Impedance Spectroscopy (EIS) techniques were employed to probe the electro-oxidation kinetics on the electrocatalyst's surface. During the EOR circumstances, the PtEu electrocatalysts showed a captivating composition-structure-activity relationship, consistent with the findings. Notably, all the physical and electrochemical analyses demonstrate that the bimetallic composition of the 84:16 electrocatalyst has shown higher EOR activity through a bifunctional mechanism. The results provide novel insights into the ethanol oxidation process over bimetallic alloy electrocatalysts, which is crucial for designing robust and efficient electrocatalysts for DEFC.

Flexible Ag@Au core–shell nanowires electrode fabrication with controllable nanogold size and thickness on silver nanowires/PDMS substrate toward enhanced ethanol electrooxidation

The synthesis of gold nanowires (AuNWs) is challenging due to difficulties in obtaining AuNWs of variable diameters and lengths. In this study, an effective approach to fabricating AuNWs with controllable lengths and diameters was developed on a flexible silver nanowires (AgNWs)/polydimethylsiloxane (PDMS) substrate. Gold nanoparticles were uniformly electrodeposited onto the flexible AgNWs/PDMS to form bimetallic Ag@Au core–shell NWs/PDMS. The results showed that the diameters and the lengths of the Ag@Au NWs were easily fine-tuned. The flexible Ag@Au NWs/PDMS electrode exhibited excellent mechanical, electrical, and electrochemical properties. In ethanol oxidation reaction (EOR), the Ag@Au NWs/PDMS achieved a peak current density of 28541.55 μA cm−2 (10 times higher than that of a commercial Au electrode) and 63.39% retaining activity in a stability test by chronoamperometry (over 2 times stable than values in literature). Finally, EOR and chromium (VI) determination by the Ag@Au NWs/PDMS in flexible integrated electrodes were performed to showcase the versatile feasibilities of this new material.

Facile Synthesis of Rhodium-Based Nanocrystals in a Metastable Phase and Evaluation of Their Thermal and Catalytic Properties.

Controlling the polymorphism of metal nanocrystals is a promising strategy for enhancing properties and discovering new phenomena. However, previous studies on Rh nanocrystals have focused on their thermodynamically stable face-centered-cubic (fcc) phase. Herein, a facile synthesis of Rh-based nanocrystals featuring the metastable hexagonal close-packed (hcp) phase is reported by using Ru seeds in their native hcp phase to template the deposition of Rh atoms. The success of such phase-controlled synthesis relies on the templating effect promoted by the small lattice mismatch between Ru and Rh and the slow dropwise titration of the precursor at an elevated temperature, ensuring the layer-by-layer growth mode and thus the formation of a conformal hcp-Rh shell. Faster injection rate of Rh(III) precursor leads to the formation of a rough Rh shell in the conventional fcc phase due to accelerated reaction kinetics. Considering both thermodynamic and kinetic aspects of this system, the hcp-Rh phase is favored when the low surface energy from smooth overlayers balances the high bulk energy of the metastable phase, achieved through tight control of reaction rates and deposition patterns. These Ruhcp@Rhhcp core-shell nanocrystals demonstrate thermal stability up to 400°C, while exhibiting higher catalytic activity toward ethanol oxidation reaction compared to Ruhcp@Rhfcc counterparts.

Stability of supported Pd-based ethanol oxidation reaction electrocatalysts in alkaline media

This study evaluates the dissolution of the supported electrocatalysts Pd/C, PdSn/C, PdNb/C, and PdFe3O4/C during ethanol oxidation reaction for Alkaline Direct Liquid Fuel Cells (ADLFC) applications. A scanning flow cell (SFC) combined to an inductively coupled plasma mass spectrometry (online ICP-MS) is used to assess the dissolution stability in a broad potential window. Accelerated stress tests with and without ethanol are developed using a rotating disk electrode (RDE) with dissolution products analysis by ex-situ ICP-MS. Potential profiles simulating those experienced by the catalyst during regular fuel cell operation were used. Sn and Fe catalysts demonstrate improved activity and stability compared with the material with Pd alone. For these reasons, PdSn/C and PdFe3O4/C are suitable for ADLFC applications. Severe Nb dissolution destabilizes Pd, increasing its leaching. This work demonstrates that while additional metals and oxides can improve the alcohol oxidation kinetics of Pd, these additives’ dissolution stability must already be considered at the catalyst design stage.

OH Regulator of Amorphous CrOx on Defect-Rich Ultrafine Pd Nanowires Boosts Electrocatalytic Ethanol Oxidation.

Reasonable construction of high activity and selectivity electrocatalysts is crucial to achieve efficient ethanol oxidation reaction (EOR). However, the oxidation of ethanol tends to produce CO species that poison the active centers of the EOR electrocatalysts. Herein, a unique amorphous CrOx-protected defect-rich ultrafine Pd nanowires (CrOx-Pd NWs) is developed. On the one hand, the CrOx layer can act as a protective layer to maintain the structure of the nanowire. On the other hand, it can play the role of OH regulator to optimize the adsorption energy barrier of intermediate species in Pd nanowire, thereby enhancing the ability of the catalyst to resist CO poisoning. The CrOx-Pd NWs exhibit excellent EOR performance with 3.64 times higher mass activity and 50mV lower CO electro-oxidation potential than commercial Pd black. The results show that the CrOx layer promotes the dissociation of H2O into OHads, while the CrOx transfers electrons to neighboring Pd atoms optimizing the electronic configuration of Pd, thus selectively oxidizing ethanol to acetate and preventing the formation of toxic *CO. This work provides an effective strategy for the synthesis of nanowire materials with oxide/metal interfaces and offers new ideas for the design of catalysts that can efficiently drive EOR.

Empowering Tri-Functional Palladium's Catalytic Activity and Durability in Electrocatalytic Formic Acid Oxidation Reaction via Innovative Self-Caging and Alloying Strategies.

Direct formic acid fuel cells (DFAFCs) stand out for portable electronic devices owing to their ease of handling, abundant fuel availability, and high theoretical open circuit potential. However, the practical application of DFAFCs is hindered by the unsatisfactory performance of electrocatalysts for the sluggish anodic formic acid oxidation reaction (FAOR). Palladium (Pd) based nanomaterials have shown promise for FAOR due to their highly selective reaction mechanism, but maintaining high electrocatalytic durability remains challenging. In this study, a novel Pd-based electrocatalyst (UiO-Pd-E) is reported with exceptional durability and activity for FAOR, which can be attributed to the Pd nanoparticles encapsulated within a carbon framework where concurrent chemical alloying of Pd and Zr occurs. Further, the UiO-Pd-E demonstrates noteworthy multifunctionality in various electrochemical reactions including electrocatalytic ethanol oxidation reaction (EOR) and oxygen reduction reaction (ORR) in addition to the FAOR, highlighting its practical potentials.

Sub-10 nm PdNi@PtNi Core–Shell Nanoalloys for Efficient Ethanol Electro-Oxidation

By controlling the structure and composition of Pt-based nanoalloys, the ethanol oxidation reaction (EOR) performances of Pt alloy catalysts can be effectively improved. Herein, we successfully synthesis sub-10 nm PdNi@PtNi nanoparticles (PdNi@PtNi NPs) with a core–shell structure by a one-pot method. The sub 10 nm core–shell nanoparticles possess more effective atoms and exhibit a synergistic effect which can lead to a shift in the d-band center and alter binding energies toward adsorbates. Due to the synergistic effect and unique core–shell structure, the PdNi@PtNi NP catalysts exhibit excellent electrocatalytic performance for ethanol oxidation reactions in alkaline, achieving 9.30 times more mass activity and 7.05 times more specific activity that of the state-of-the-art Pt/C catalysts. Moreover, the stability of PdNi@PtNi NPs was also greatly improved over PtNi nanoparticles, PtPd nanoparticles, and commercial Pt/C. This strategy provides a new idea for improving the electrocatalytic performance of Pt-based catalysts for EORs.

Construction of Multiphase Concave Tetrahedral PdInMo Nanocatalyst for Enhanced Alcohol Oxidation

AbstractHeterogeneous palladium‐based catalysts show excellent catalytic properties for electrocatalytic oxidation of alcohols, but the construction of such heterogeneous catalysts is a challenge. Here, a multiphase tetrahedral PdInMo nanocatalyst is prepared by a one‐pot reaction method. And the multiphase tetrahedral PdInMo nanocatalyst consists of a face‐centered cubic structure and an intermetallic structure. Due to the oxygen affinity of indium and molybdenum atoms, the interface defects of internal multiphase structure, and intermetallic structure, the multiphase concave tetrahedral PdInMo nanocatalyst shows enhanced catalytic efficiency in the electrocatalytic oxidation reaction of methanol and ethanol. Compared with commercial Pd/C catalysts, PdIn0.117Mo0.037 nanocatalyst has the best mass activity and specific activity. In electrocatalysis of methanol oxidation, the mass activity (2205.57 mA mgPd−1) and specific activity (6.67 mA cm−2) are 4.81 and 3.40 times than that of a commercial Pd/C nanocatalyst (458.5 mA mgPd−1, 1.96 mA cm−2), respectively. In the electrocatalysis of ethanol oxidation, the mass activity (2668.49 mA mgPd−1) and specific activity (8.11 mA cm−2) are 4.06 and 3.14 times than that of the commercial Pd/C nanocatalyst (655.83 mA mgPd−1, 2.58 mA cm−2), respectively. This study provides a reference for the design of highly efficient palladium catalysts for alcohol oxidation.

PtCu-a-SnO2 interface engineering on PtCu-SnO2 aerogels for ethanol oxidation electrocatalysis

Designing catalysts with high activity and stability to boost their ethanol oxidation reaction (EOR) performance is one of the central targets in the development of direct ethanol fuel cells (DEFCs). However, how to design the EOR catalysts in a rational way is still challenging, needing more efforts put in. Herein, we have synthesized a catalyst of PtCu-SnO2 aerogel via ingeniously introducing Cu into Pt-SnO2 system, resulting in the formation of a main phase of alloy (PtCu)-amorphous oxide (a-SnO2) interface. Benefiting from the optimized structures, the PtCu-SnO2 aerogel displays excellent acidic EOR performance with 4.5 times promotion in activity compared to pure Pt aerogel. In-depth investigations through electrochemical in-situ Fourier transform infrared spectroscopy and density functional theory calculations have shown that the absorbed OH on a-SnO2 surface together with the greatly-modified electronic structure of the alloy surface atoms can facilitate the C1 pathway and the oxidation of *CO intermediates for ethanol oxidation reaction. The resulting affinity of surface OH and the modification of reaction energies both in turn contribute to the improvement of EOR performance with high activity, stability, and anti-poisoning ability, proving interfacial engineering an effective strategy for the rational design of EOR catalyst.

Three-component NiO/Fe3O4/rGO nanostructure as an electrode material towards supercapacitor and alcohol electrooxidation

A nanocomposite made of nickel oxide and iron oxide (NiO/Fe3O4) and its hybrid with reduced graphene oxide (rGO) as a conductive substrate with a highly functional surface (NiO/Fe3O4/rGO) was synthesized using a simple hydrothermal approach. This study addresses the challenge of developing efficient materials for energy storage and alcohol fuel cells. After confirming the synthesis through structural analysis, the potential of these nanocomposites as supercapacitor electrodes and catalysts for methanol and ethanol oxidation in alcohol fuel cells were evaluated. The synergy of combining the two metal oxides and adding rGO to the composite structure led to excellent electrocatalytic activity in alcohol oxidation. For the modified NiO/Fe3O4/rGO electrode in the methanol oxidation reaction (MOR), a current density of 450 mA/cm2 at 0.67 V and excellent catalyst stability of 98.7 % over 20 h in chronoamperometric analysis were observed. In the ethanol oxidation reaction (EOR), an oxidative current of 235 mA/cm2 at a peak potential of 0.76 V was seen, with catalyst stability of 96.4 % after 20 h. As a supercapacitor electrode, the NiO/Fe3O4 composite demonstrated a specific capacitance of 946 F/g, while NiO/Fe3O4/rGO showed 1155 F/g. The stability of these electrodes after 10000 GCD cycles was 83.6 % and 90.6 %, respectively. These findings suggest that the proposed structures are cost-effective and reliable alternatives for energy storage and production, suitable for alcohol fuel cells and supercapacitors.

Atomically dispersed NiOx cluster on high-index Pt facets boost ethanol electrooxidation through long-range synergistic sites

Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications. Herein, the concept of holding atomically dispersed NiOx cluster supported on Pt-based high-index facets (NiOx/Pt) is proposed to build O-bridged Pt–Ni dual sites. Strikingly, the obtained NiOx/Pt dual sites show 4.97 times specific activity higher than that of commercial Pt/C (0.35 ​mA ​cm−2), as well as outstanding CO-tolerance and durability. The advanced electrochemical in-situ characterizations reveal that the NiOx/Pt can accelerate rapid dehydroxylation and C–C bond-cleavage over the Pt–Ni dual sites. Theoretical calculations disclose that the atomically dispersed NiOx species can lower the adsorption/reaction energy barriers of intermediates. This tactic provides a promising methodology on regulating the surface synergistic sites via engineering atomically dispersed oxide site.

Ethanol Oxidation Reaction on Electrodeposited Pd and Sb‒Pd Catalysts in Alkaline Solution Containing Na or Li Cations

Abstract This work reports the galvanostatical electrodeposition of Pd and Sb‒Pd catalysts on rotating glassy carbon (GC) electrode using surfactant-free electrolytes and the prepared catalysts were tested is the electro-oxidation reactions in alkaline solutions. Characterization of Pd and Sb‒Pd catalysts was performed with scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) technique. Cyclic voltammetry (CV) and chronoamperometry were applied in order to study the electrocatalytic behavior of Pd and Sb‒Pd catalysts in the ethanol oxidation reaction (EOR) in alkaline solution containing Na+ or Li+ cations from the point of the impact of the selected alkali metal cations on the electrocatalytic activity. The peak current of EOR at Pd and Sb‒Pd catalysts in the solution with Li+ cations is 2.5 times higher compared to the values obtained in the solution with Na+ cations. EOR starts at rather negative potentials in LiOH solution regarding NaOH for approximately 0.03 V indicating the active role of OHad and the impact of the nature of alkali metal cations which consequently arises from the formation of OHad ‒ cation clusters. The role of Sb in bimetallic catalyst was established by adjusting the extent and persistence of OHad surface coverage.

Laser Irradiation Induced Electronic Structure Modulation of the Palladium-Based Nanosheets for Efficient Electrocatalysts.

Palladium nanosheets (Pd NSs) are widely used as electrocatalysts due to their high atomic utilization efficiency, and long-term stability. Here, the electronic structure modulation of the Pd NSs is realized by a femtosecond laser irradiation strategy. Experimental results indicate that laser irradiation induces the variation in the atomic structures and the macrostrain effects in the Pd NSs. The electronic structure of Pd NSs is modulated by laser irradiation through the balancing between Au-Pd charge transfer and the macros-strain effects. Finite element analysis (FEA) indicates that the lattice of the nanostructures undergoes fast heating and cooling during laser irradiation. The structural evolution mechanism is disclosed by a combined FEA and molecule dynamics (MD) simulation. These results coincide well with the experimental results. The L-AuPd NSs exhibit excellent mass activity and specific activity of 7.44 A mg-1 Pd and 18.70mA cm-2 toward ethanol oxidation reaction (EOR), 4.3 and 4.4 times higher than the commercial Pd/C. The 2500-cycle accelerated durability (ADT) test confirms the outstanding catalytic stability of the L-AuPd NSs. Density functional theory (DFT) calculations reveal the catalytic mechanism. This unique strategy provides a new pathway to design the ultrathin nanosheet-based materials with excellent performance.