Direct Ethanol Research Articles

PtNiRu/SnO2 Nanoframes as Anodic Catalyst for Direct Ethanol Fuel Cells

PtNiRu/SnO₂ Nanoframes as Anodic Catalyst for Direct Ethanol Fuel Cells

3D hollow superstructures endow PdAg electrocatalyst with selective ethanol electrooxidation

Direct ethanol fuel cells (DEFCs) have been considered as future power devices for many portable applications. The ethanol oxidation reaction (EOR), that is, a multielectron process, suffers from low efficiency owing to the high selectivity to the 4e− pathway (C2 pathway) and low selectivity to the 12e− pathway (C1 pathway). The preparation of efficient catalysts with high C1 pathway selectivity is regarded as a promising and fascinating field. Herein, we first advance a one-pot synthesis of 3D PdAg superstructures (SSs) with a hollow interior and ultrathin nanosheet shell. PdAg SSs achieve a mass activity of 5.27 A mg−1 for the alkaline EOR and a Faraday efficiency of 22.7 % for the C1 pathway, which is 5.7 and 7.5 times higher than that of commercial Pd/C, respectively. Mechanism studies confirm that the construction of the Pd-Ag system greatly facilitates the oxidation of the C1 intermediates (*CH3 and *CO) and enhances the CC bond cleavage ability of the catalyst. This work not only highlights an active Pd-based catalyst for the selective EOR, but also sheds light on the formation of 3D open nanostructure via self-assembly of 2D nanosheets.

Influence of Anode Diffusion Layer on the Performance of a Passive Direct Ethanol Fuel Cell

One of the main challenges with passive direct ethanol fuel cells (DEFCs) is ethanol transport management since the liquid ethanol is supplied to the anode compartment by natural processes including convection and diffusion with a low cell operating condition. The significant layer in the cell is the diffusion layer (DL), which facilitates reactants to reach the anode catalyst layer (CL). In this study, the impact of various DLs fabricated of readily accessible commercial materials on cell performance in passive DEFCs with different ethanol feed concentrations was examined with various in-situ characterization methods. The results demonstrate that the cell with a DL coated by the hydrophobic microporous layer (MPL) yielded the best performance of 0.887 mW·cm-2 at the optimal ethanol feed concentration of 5 M. In conclusion, the benefits of enhancing ethanol mass transfer to the anode CL would outweigh the drawbacks of preventing ethanol crossover to the cathode. HIGHLIGHTS The effect of the anode diffusion layer (DL) on passive direct ethanol fuel cell (DEFC) performance was determined Five different anode DLs fabricated of readily accessible commercial materials were employed Various characterizations enabled the assessment of each loss affecting the passive DEFC performance The cell with an anode DL modified with a hydrophobic microporous layer (MPL) exhibited the best cell performance The optimal ethanol feed concentration of the best cell was found to be 5 M GRAPHICAL ABSTRACT

D-Band Engineering in Pd-Based Nanowire Networks for Further Enhancement in Ethanol Electrooxidation Reaction.

The development of highly efficient electrocatalysts for the ethanol oxidation reaction (EOR) is essential for the commercialization of direct ethanol fuel cells, yet challenges remain. In this study, a one-pot solution-phase method to synthesize Pd nanowire networks (NNWs) with very high surface-to-volume ratio having numerous twin and grain boundaries is developed. Using the same method, the Pd lattice is further engineered by introducing Ag and Cu atoms to produce AgPd, and CuPd alloy structure which significantly shifts the Pd d-band center upward and downward, respectively due to strain and ligand effects. Theoretical analysis employing density functional theory (DFT) demonstrates that such modification of the d-band center significantly influences the adsorption energies of reactants on the catalytic surface. Owing to their notably high surface-to-volume ratio and the presence of multiple twin and grain boundaries, Pd NNWs demonstrate significantly enhanced electrocatalytic activity toward EOR, ≈7.2 times greater than that of commercial Pd/C. Remarkably, compared to Pd NNWs, AgPd, and CuPd NNWs display enlarged and reduced electrocatalytic activity toward EOR, respectively. Specifically, Ag4Pd7 NNWs achieve a remarkable mass activity of 9.00Amgpd -1 for EOR, which is 13.6 times higher than commercial Pd/C.

Facile construction of core-shell AuPd nanochain networks in one-pot for ethanol oxidation

Palladium (Pd)-based catalysts have been extensively investigated in direct ethanol fuel cells (DEFCs) since the urgent energy and environmental problems. Rational design Pd-based catalyst with outstanding structure can optimize its electrocatalytic performance for ethanol oxidation reaction (EOR) catalyst. In this work, a facile strategy was proposed to prepare AuPd nanochain networks (NNWs) with core-shell structure by adjusting the reduction rate by slowly dropping the acidic reducing agent to the alkaline precursor solution system. The resulting catalysts exhibit a porous self-supporting structure with twisted features, exposing a large number of active sites. The optimized AuPd NNWs catalyst displays much-improved activity (3289.62 mA mg−1 Pd) and greatly enhanced electrocatalytic stability for EOR in comparison with that of commercial Pd/C catalysts. This enhanced activity can be attributed to the synergic effect of the Pd shell with the Au core as well as the twisted and self-supporting structure which can expose much more active sites and provide rich mass and electron transfer channels.

Evaluation of harmful drinking among professional drivers by direct ethanol biomarkers and its relation with psychological distress

Objective This study aimed to evaluate the alcohol consumption among professional truck and bus drivers using direct ethanol biomarkers, and to explore its relationship with anxiety, depression, and stress. Methods The assessment of potential harmful drinking was conducted through the measurement of direct biomarkers: phosphatidylethanol (PEth), ethyl glucuronide (EtG), and ethyl sulfate (EtS), using dried blood spots (DBS). Additionally, self-reported data from the Alcohol Use Disorders Identification Test (AUDIT-C) were used. Emotional states, including depression, anxiety, and stress, were evaluated using the Depression, Anxiety, and Stress Scale (DASS-21). Results A total of 97 drivers participated in the study, with the majority being male (96%) and identified as truck drivers (75.3%). Among them, 43.3% reported working more than 10 h daily. The majority of volunteers exhibited normal levels of stress (81.4%), anxiety (83%), and depression (86.6%). According to the AUDIT-C assessment, 30.9% were categorized as having a moderate risk, while 11.3% were deemed to be at high risk for harmful alcohol consumption behavior. Ethyl glucuronide (EtG) and ethyl sulfate (EtS) levels, indicating recent ethanol consumption, were detected in 14.4% of the drivers. In contrast, the long half-life metabolite PEth (16:0-18:1) was present in 88.7% of the volunteers. A moderate correlation (rs = 0.45, p < .01) was observed between PEth levels and AUDIT-C scores. The Receiver Operating Characteristic (ROC) curve, utilizing a PEth threshold of ≥ 59.0 ng ml−1, displayed 78% sensitivity and 73% specificity in effectively distinguishing high risk for alcohol intake. Notably, no significant associations were found between alcohol consumption and levels of stress, depression, and anxiety. Conclusions The study findings indicate a noteworthy proportion of drivers engaging in regular alcohol consumption alongside a demanding workload. Notably, PEth measurements highlighted an underreporting within the AUDIT-C self-reports. These results lend robust support for the utilization of biomarkers in assessing alcohol consumption patterns among drivers.

Palladium/coconut husk biochar composite material as an effective electrocatalyst for ethanol oxidation reaction

This study utilised coconut husk biochar as an alternative sustainable carbon support for Pd-based electrocatalyst for ethanol oxidation reaction in basic medium. Coconut husk biochar (BC) was prepared via slow pyrolysis at 800 °C for 1 h at a ramp rate of 5 °C min−1. The Pd/BC catalyst was prepared via borohydride-facilitated reduction of palladium chloride solution. TEM analysis revealed good dispersion of the Pd nanoparticles on the biochar support with particle size ranging from 1.9 to 3.4 nm. Cyclic voltammetry (CV) measurements of Pd/BC in 1.0 M ethanol in 0.1 M KOH gave an on-set potential of −0.615 V (versus Ag/AgCl) with a forward peak current density of 23.87 mA cm−2, which is slightly higher than the commercial Pd/C catalyst. The Pd/BC also has a higher electrochemical stability and durability than the commercial Pd/C catalyst based on chronoamperometry studies (i.e., 44.43% versus 39.64% current retention). The synthesised coconut husk biochar–supported Pd catalyst exhibited promising results for ethanol oxidation reaction for alkaline direct ethanol fuel cell application.

Laser Irradiation Synthesis of AuPd Alloy with Decreased Alloying Degree for Efficient Ethanol Oxidation Reaction.

The preparation of electrocatalysts with high performance for the ethanol oxidation reaction is vital for the large-scale commercialization of direct ethanol fuel cells. Here, we successfully synthesized a high-performance electrocatalyst of a AuPd alloy with a decreased alloying degree via pulsed laser irradiation in liquids. As indicated by the experimental results, the photochemical effect-induced surficial deposition of Pd atoms, combined with the photothermal effect-induced interdiffusion of Au and Pd atoms, resulted in the formation of AuPd alloys with a decreased alloying degree. Structural characterization reveals that L-AuPd exhibits a lower degree of alloying compared to C-AuPd prepared via the conventional co-reduction method. This distinct structure endows L-AuPd with outstanding catalytic activity and stability in EOR, achieving mass and specific activities as high as 16.01 A mgPd-1 and 20.69 mA cm-2, 9.1 and 5.2 times than that of the commercial Pd/C respectively. Furthermore, L-AuPd retains 90.1% of its initial mass activity after 300 cycles. This work offers guidance for laser-assisted fabrication of efficient Pd-based catalysts in EOR.

The Role of Cytokines in the Pathogenesis and Treatment of Alcoholic Liver Disease.

Alcoholic liver disease (ALD) is a major cause of chronic liver disease. This term covers a broad spectrum of liver lesions, from simple steatosis to alcoholic hepatitis and cirrhosis. The pathogenesis of ALD is multifactorial and not fully elucidated due to complex mechanisms related to direct ethanol toxicity with subsequent hepatic and systemic inflammation. The accumulation of pro-inflammatory cytokines and the reduction of anti-inflammatory cytokines promote the development and progression of ALD. To date, there are no targeted therapies to counter the progression of chronic alcohol-related liver disease and prevent acute liver failure. Corticosteroids reduce mortality by acting on the hepatic-systemic inflammation. On the other hand, several studies analyzed the effect of inhibiting pro-inflammatory cytokines and stimulating anti-inflammatory cytokines as potential therapeutic targets in ALD. This narrative review aims to clarify the role of the main cytokines involved in the pathogenesis and treatment of ALD.

Defect-rich PdCo bimetallene constructed by a self-reduction strategy for enhanced ethanol oxidation reaction

Direct ethanol fuel cells have garnered considerable attention owing to their minimal pollution, high energy density and diverse fuel sources. However, the slow anodic ethanol oxidation reaction has limited its large-scale application. In this work, the green self-reduction method of Co2(CO)8 as precursor and reducing agent is used to design PdCo bimetallene for ethanol oxidation reaction. The ultra-thin porous nanosheet structure of PdCo bimetallene leads to its abundant defects, facilitating increased active sites and enhanced electrical conductivity. The findings demonstrate substantial enhancements in both the activity and stability of the catalyst. The mass activity of PdCo bimetallene reached 1.58 A mg−1, marking a 2.8-fold increase compared to Pd black. Moreover, the catalyst maintained no less than 98% of the initial current over five consecutive 4000 s chronoamperometric tests, highlighting its remarkable stability. This work provides a green self-reduction synthesis strategy for the preparation of defect-rich bimetallene for ethanol electrocatalytic applications.

Porous hemispherical Au@PdAg catalysts for enhancing ethanol electrooxidation

Direct ethanol fuel cell can convert chemical energy into electric energy directly, and has the advantages of being free from Carnot cycle and being friendly to environment, so it has a broad application prospect. However, the insufficient activity and toxicity resistance of anodic catalysts limit their commercial application, mainly due to the limited adsorption sites and the toxic inactivation of catalysts resulting from the production of toxic intermediates (COads) during the ethanol oxidation reaction (EOR) process. In this study, the Au@PdAg porous hemispherical catalyst assembled by nanotubes was successfully prepared by soft template method and co-reduction method using dioctadecyl dimethyl ammonium chloride (DODAC) as surfactant, and its EOR performance was tested. Au@Pd1.0Ag1.0 has the highest mass current density with a peak value of 4048.8 mAmgPd−1, which is 7.8 times of Pd/C (JM). After 5000 s stability test, the residual current density value is still 863.4 mAmgPd−1. The results showed that the introduction of the oxygenophilic metal Ag was conducive to the formation of OHads and the oxidation of COads. The porous structure of the nanotube assembly facilitates electron transfer and provides more adsorption sites, which makes the catalyst show good electrocatalytic activity and anti-CO poisoning ability.

Direct Ethanol Fuel Cell for Clean Electric Energy: Unravelling the Role of Electrode Materials for a Sustainable Future

Direct ethanol fuel cells (DEFCs) are better than others in commercially used FCs due to easy availability, less toxicity, and C‐2‐type alcohol. Ethanol has a high theoretical efficiency of 97% and is a safe, plentiful, and renewable resource that can be stored and controlled using the infrastructure that is in place now. Nevertheless, low functional efficiencies and the release of carbon dioxide (CO2), acetaldehyde, and byproducts of acetic acid must be addressed if DEFCs are to grow and become more commercially viable. To overcome these problems, new anode and cathode catalysts are needed, so this review article discusses the introduction of FCs with their structure, working and mechanism. Further, the report covers various types of FC catalysts, and their application in FC technology is explained. The role of the catalyst (such as anode and cathode), similarities and differences between Pt/Pd‐based catalysts, and the importance of supporting materials (such as carbon, transition metal dichalcogenides, MXene, and black phosphorus‐based materials) in DEFCs are described. In addition, the applications, advantages, and disadvantages of the DEFCs are discussed. Finally, the proposed theme is concluded with the existing challenges in this field and the future prospect of DEFCs.

Interface Engineering of PdPt Ultrafine Ethanol Electro-Oxidation Nanocatalysts by Bacterial Soluble Extracellular Polymeric Substances (s-EPS) to Break through Sabatier Principle.

Unsatisfactory performance of ethanol oxidation reaction (EOR) catalysts hinders the application of direct ethanol fuel cells (DEFCs), while traditional alloy catalysts (like PdPt) is cursed by Sabatier principle due to countable active site types. However, bacterial soluble extracellular polymeric substances (s-EPS) owning abundent functional groups may help breacking through it by contrusting different active sites on PdPt and inducing them to play synergy effect, which is called interface engineering. Using s-EPS to engineer catalysts is more green and consumes lower energy compared to chemical reagents. Herein, PdPt alloy nanoparticles (≈2.1nm) are successfully in situ synthesized by/on s-EPS of Bacillus megaterium, an ex-holotype. Tryptophan residuals are proved as the main reductant. In EOR, PdPt@s-EPS shows higher activity (3.89mAcm-2) than Pd@s-EPS, Pt@s-EPS, Pt/C and most reported akin catalysts. Its stability and durability are excellent, too. DFT modelling further demonstrates that, interface engineering by s-EPS breaks through Sabatier principle, by the synergy of diverse sites owning different degrees of d-p orbital hybridization. This work not only makes DEFCs closer to practice, but provides a facile and green strategy to design more catalysts.

RhCuBi Trimetallenes with Composition Segregation Coupled Crystalline‐Amorphous Heterostructure Toward Ethanol Electrooxidation

AbstractThe inefficiency of Pt and Pd benchmark catalysts in achieving complete ethanol oxidation, coupled with their inherent susceptibility to poisoning, poses a significant obstacle to the advancement of direct ethanol fuel cells. In this study, the development of self‐supported and ultrathin RhCuBi trimetallenes, demonstrating exceptional performance in ethanol electrooxidation through segregation and interface engineering is presented. The distinctive RhBi‐rich crystalline/RhCu‐rich amorphous heterostructure of RhCuBi trimetallenes creates a wealth of highly active interfacial sites for the ethanol oxidation reaction (EOR). This results in an impressive 43.3% Faradaic efficiency for the C1 pathway and a peak mass activity of 1.11 A mgRh−1 at 0.68 V versus reversible hydrogen electrode. Moreover, RhCuBi trimetallenes retain 60% of their initial mass activity after 8.5 h of constant potential electrolysis, outperforming commercial Pd and Pt catalysts (&lt;3%). In/ex situ infrared spectroscopy directly reveals the generated C1 products and the key CH3CO* intermediates for EOR on RhCuBi trimetallenes. Theoretical calculations confirm that the RhBi alloy, particularly the lattice‐stretched crystalline/amorphous interfacial sites, facilitates the adsorption/activation of ethanol and the dehydrogenation of CH3CO* toward the C1 pathway of EOR. This breakthrough offers promising prospects for enhancing the efficiency and stability of ethanol electrooxidation in fuel cell applications.

Experimental investigation on a novel empirical parameter for simultaneous analysis of the temperature and concentration effects on fuel utilization coefficient of direct ethanol fuel cell

In this study, a DEFC with an anion-exchange membrane is investigated to evaluate fuel utilization both theoretically and experimentally. The effects of variations in the input fuel temperature and fuel concentration on fuel utilization and power density were analyzed through sensitivity analysis. To this end, for different test conditions containing initial conditions, increasing the input fuel temperature and oxygen blowing to the cathode with fuel circulation, ethanol utilization factor and maximum power density were calculated. The findings revealed increasing the fuel temperature and oxygen blowing led to an increase in the ethanol utilization factor from 66.92% to 85.15% and 73.54%. Moreover, maximum power density was increased from 16.2 to 17.5 and 22.5 mWcm−2 for increasing the fuel temperature and oxygen blowing states. According to the results, it was proved that increasing the input fuel temperature and oxygen-blowing conditions had a contradictory impact on the performance analysis. As a solution, a new parameter named δ is introduced to conduct a more accurate performance analysis of DEFC. This parameter indicates the amount of produced power per unit of fuel consumption. The results demonstrated that parameter δ was increased from 0.14 to 0.21 and 0.31 mWcm−2 for increasing the fuel temperature and oxygen blowing states.

Recent Approaches for Cleaving the C─C Bond During Ethanol Electro-Oxidation Reaction.

Direct ethanol fuel cells (DEFCs) play an indispensable role in the cyclic utilization of carbon resources due to its high volumetric energy density, high efficiency, and environmental benign character. However, owing to the chemically stable carbon-carbon (C─C) bond of ethanol, its incomplete electrooxidation at the anode severely inhibits the energy and power density output of DEFCs. The efficiency of C─C bond cleaving on the state-of-the-art Pt or Pd catalysts is reported as low as 7.5%. Recently, tremendous efforts are devoted to this field, and some effective strategies are put forward to facilitate the cleavage of the C─C bond. It is the right time to summarize the major breakthroughs in ethanol electrooxidation reaction. In this review, some optimization strategies including constructing core-shell nanostructure with alloying effect, doping other metal atoms in Pt and Pd catalysts, engineering composite catalyst with interface synergism, introducing cascade catalytic sites, and so on, are systematically summarized. In addition, the catalytic mechanism as well as the correlations between the catalyst structure and catalytic efficiency are further discussed. Finally, the prevailing limitations and feasible improvement directions for ethanol electrooxidation are proposed.

Interfacial Electronic Interactions within the Pd-CeO2/Carbon Onions Define the Efficient Electrocatalytic Ethanol Oxidation Reaction in Alkaline Electrolytes.

Porous Pd-based electrocatalysts are promising materials for alkaline direct ethanol fuel cells (ADEFCs) and ethanol sensors in the development of renewable energy and point-of-contact ethanol sensor test kits for drunk drivers. However, experimental and theoretical investigations of the interfacial interaction among Pd nanocrystals on supports (i.e., carbon black (CB), onion-like carbon (OLC), and CeO2/OLC) toward ADEFC and ethanol sensors are not yet reported. This is based on the preparation of Pd-CeO2/OLC nanocrystals by the sol-gel and impregnation methods. Evidently, the porous Pd-CeO2/OLC significantly increased membrane-free micro-3D-printed ADEFC performance with a high peak power density (Pmax = 27.15 mW cm-2) that is 1.38- and 7.58-times those of Pd/OLC (19.72 mW cm-2) and Pd/CB (3.59 mW cm-2), besides its excellent stability for 48 h. This is due to the excellent interfacial interaction among Pd, CeO2, and OLC, evidenced by density functional theory (DFT) simulations that showed a modulated Pd d-band center and facile active oxygenated species formation by the CeO2 needed for ethanol fuel cells. Similarly, Pd-CeO2/OLC gives excellent sensitivity (0.00024 mA mM-1) and limit of detection (LoD = 8.7 mM) for ethanol sensing and satisfactory recoveries (89-108%) in commercial alcoholic beverages (i.e., human serum, Amstel beer, and Nederberg Wine). This study shows the excellent possibility of utilizing Pd-CeO2/OLC for future applications in fuel cells and alcohol sensors.

Palladium nanoparticles integrated ternary nickel cobalt iron hydroxide as an efficient bifunctional electrocatalyst for direct ethanol fuel cell

The rational design and identification of the underlying role of the support materials to promote the electrocatalytic activity of the active catalyst are the main objectives of the current research. Herein, we synthesized different compositions of ternary nickel cobalt iron transition metal hydroxide (TMH) supported palladium (Pd) nanoparticles (Pd/Hy) to improve the ethanol electrooxidation reaction (EOR) and oxygen reduction reaction (ORR) kinetics of Pd NPs. The TMH supports modified the surface electronic structures of Pd through strong metal support interaction, thereby improving the EOR and ORR reaction kinetics. Herein, we explored potential-dependent electrochemical impedance spectroscopy (EIS) to identify the intermediates species formed during the ORR and EOR process and rationalize the reaction mechanism. The potential-dependent EIS reveals that TMH supports eliminating the adsorption of the poisonous carbonaceous species during the EOR. The synthesized bifunctional Pd/Hy catalyst integrated alkaline direct ethanol fuel cell device exhibits a peak power density of 28.1 mW/cm2, which is a higher performance than that of the Pt/C integrated devices. Finally, Pd/Hy catalyst-integrated passive DEFC was tested, and a portable electronic application was demonstrated.

Energy conversion using Pd-based catalysts in direct ethanol fuel cell

Direct Ethanol Fuel Cells DEFCs are considered one of the promising renewable energy sources, as they can produce electrical energy directly from the ethanol electrooxidation reaction. The efficiency of ethanol electrooxidation is a big question from research point of view. In this work, Pd is used as catalyst for the electrooxidation in alkaline media aiming to improve the catalytic activity for ethanol electrooxidation reaction, and consequently the DEFC performance, more than using a Pt-based catalyst. In this research, Pd was used as an alternative for Pt-based catalyst. Additionally, it can be recorded that the alloying of Pd with Sn will enhance the efficiency through increasing the surface area of the PdSn catalysts.

Enhanced electrocatalytic activity of palladium electrocatalysts supported on corncob biochar for ethanol oxidation reaction in alkaline medium

AbstractIn this study, palladium particles supported on carbon black (Vulcan XC‐72) (Pd/C) and corncob biochar (Pd/CB800, Pd/CB900, and Pd/CB1000) were successfully synthesized using borohydride reduction. The biochar support was obtained from corncob waste via pyrolysis from 800 to 1000°C. Scanning electron microscopy with energy dispersive x‐ray (SEM–EDX) revealed successful deposition of Pd metal particles on the carbon support materials. X‐ray diffraction (XRD) analysis confirmed the crystalline structures of Pd, and the crystallite size was found to be smallest in Pd/CB900. The electrocatalytic activity of the Pd electrocatalyst composites towards ethanol oxidation reaction (EOR) in an alkaline medium was investigated using cyclic voltammetry (CV). CV analysis has shown that Pd/CB900 gave the least positive onset potential (Eonset = −0.587 ± 0.0065 V), highest electrochemically active surface area (EASA = 31.51 ± 2.24 m2·g−1), and highest anodic peak current density (If = 20.77 mA·cm−2) compared with Pd/CB800, Pd/CB1000, and Pd/C. Furthermore, the Tafel plot and chronoamperometry have shown that Pd/CB900 exhibited faster kinetics (Tafel slope = 297.6 ± 4.62 mV·dec−1) and durability (% current retention = 50.64 ± 2.99%) than Pd/C towards EOR in an alkaline medium. This study highlights the simple and straightforward synthesis of the anode electrocatalyst material for direct ethanol fuel cell application.