CO Tolerance Research Articles

Enhancement of non-oleaginous green microalgae Ulothrix for bio-fixing CO2 and producing biofuels by ARTP mutagenesis.

Oleaginous green microalgae are often mentioned in algae-based biodiesel industry, but most of them belong to specific genus (Chlorella, Scenedesmus, Botryococcus and Desmodesmus). Thus, the microalgal germplasm resources for biodiesel production are limited. Mutagenesis is regarded as an important technology for expanding germplasm resources. The main purpose of this study is to screen microalgae strains with high carbon dioxide tolerance and high lipid content from mutants derived from indigenous non-oleaginous green microalgae species-Ulothrix SDJZ-17. Two mutants with high CO2 tolerance and high lipid content genetic stability were obtained from the mutants by high-throughput screening, named Ulothrix SDJZ-17-A20 and Ulothrix SDJZ-17-A23. In order to evaluate the potential of CO2 fixation and biofuel production, A20 and A23 were cultured under air and 15% CO2 (v/v) conditions, and their wild-type strains (WT) were used as controls. Under the condition of high CO2 concentration, the growth performance and lipid production capacity of mutant strains A20 and A23 were not only significantly better than those of wild strains, but also better than those of their own cultured under air conditions. Among them, A23 obtained the highest LCE (light conversion efficiency) (14.79%), Fv/Fm (maximal photochemical efficiency of photosystem II) (71.04%) and biomass productivity (81.26mgL-1d-1), while A20 obtained the highest lipid content (22.45%). Both mutants can be used as candidate strains for CO2 fixation and biofuel production. By ARTP (atmospheric and room temperature plasma) mutagenesis with high-throughput screening, the mutants with higher CO2 tolerance, photosynthetic efficiency and lipid productivity can be obtained, even if they are derived from non-oleaginous microalgae, which is of great significance for enriching the energy microalgae germplasm bank, alleviating the global warming and energy crisis.

High-entropy perovskite (Pr1/6Nd1/6Sm1/6Ba1/6Sr1/6)6/7(Mn1/6Co)6/7O3-δ as a highly active and CO2 durable cathode for solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are environmentally friendly energy conversion devices that convert the chemical energy in fuels directly into electrical power. The development of high-catalytic activity and durability cathode materials is crucial for the commercialization of SOFCs. Herein, a novel A-site deficient high-entropy perovskite oxide (Pr1/6Nd1/6Sm1/6Ba1/6Sr1/6)6/7(Mn1/6Co)6/7O3-δ (PNSBSMC) was designed. The strong disorder effect associated with entropy increase in high-entropy perovskite oxide is anticipated to accelerate oxygen reduction reaction (ORR) kinetics. PNSBSMC demonstrates excellent catalytic activity for oxygen reduction, primarily due to the entropy-driven enhancement that promotes oxygen adsorption, dissociation, and charge transfer dynamics. The increase in entropy not only significantly mitigates the thermal expansion of PNSBSMC but also provides additional pathways for ionic/electronic transport. At 800 °C, the PNSBSMC-based single cell achieved a remarkable peak power density of 1.41 W cm−2, representing an 88.0 % improvement over the single-phase PBC. Additionally, PNSBSMC demonstrates superior performance stability and CO2 tolerance. These findings suggest that high-entropy PNSBSMC perovskite holds significant potential as an effective cathode for SOFCs. This study offers new insights for the future development of high-stability, high-activity SOFC cathode materials.

Enhancing CO tolerance in hydrogen oxidation reaction through synergy of surface-modified MoOx with PtRu alloy

Even trace amounts of CO impurities present in low-cost crude hydrogen can severely poison Pt-based catalysts. For proton exchange membrane fuel cells (PEMFCs), the development of hydrogen oxidation reaction (HOR) catalysts capable of enduring CO contamination is of significant economic importance. In this study, we propose a new strategy to synergistically enhance the CO tolerance of PtRu alloys by incorporating MoOx. The MoOx modified on PtRu/C catalysts can initiate the oxidation of CO adsorbed on its surface at potentials as low as 0.125 V. The synergy effect of MoOx and bifunctional PtRu ensures sufficient HOR stability even under hydrogen containing high CO concentrations. The resulting PtRu-MoOx/C catalyst exhibits a 4.6-fold increase in remained HOR current compared to commercial PtRu/C, after two hours in a hydrogen environment containing 10,000 ppm CO. Under typical testing condition of H2/1,000 ppm CO, PtRu-MoOx/C maintains over 80 % of the initial current density even after ten hours, significantly outperforming PtRu/C (30 %) and most previously reported catalysts.

Temperature-controlled in-situ construction of composition-tunable nanoparticle-decorated SOFC cathodes with enhanced oxygen reduction kinetics and CO2 tolerance

High oxygen reduction reaction (ORR) catalytic activity and CO2 resistance of the cathode are fundamental to the commercial application of solid oxide fuel cells (SOFCs). Therefore, we develop a temperature-driven reduction-reoxidation strategy to in-situ construct heterostructured perovskite cathodes decorated with different nanoparticles by controlling the reduction temperature. For (Pr0.4Sr0.6)0.95Co0.2Fe0.8-xNixO3-δ (PSCFN, x = 0.05, 0.1), reduction (@700 °C)-reoxidation results in the exsolution of a ComFenNi3-m-nO4 spinel phase on the perovskite scaffold surface, while reduction (@750 °C)-reoxidation leads to the formation of both ComFenNi3-m-nO4 spinel phase and NiO nanoparticles. The exsolution of these highly active species increases the quantity of oxygen reduction active sites and effectively suppresses Sr segregation. The simultaneous formation of ComFenNi3-m-nO4 spinel phase and NiO nanoparticles induces B-site ion vacancies in the main phase, therefore facilitates the formation of oxygen vacancies. Additionally, the presence of ComFenNi3-m-nO4/NiO/PSCFN heterointerfaces promotes oxygen adsorption and transfer. The strong interactions among ComFenNi3-m-nO4, NiO, and PSCFN significantly enhance the structural stability. At 800 °C, Reo2-PSCFN0.1 achieves an output performance of 1.12 W cm−2, representing a 36.6 % enhancement compared to PSCFN0.1. Moreover, the Rp of Reo2-PSCFN0.1 is merely 0.0186 Ω cm2, marking a 40.4 % decrease relative to PSCFN0.1. This temperature-driven reduction-reoxidation strategy shows great promise as a novel approach for creating high-performance IT-SOFC cathodes.

Pt Nanoparticles on Multi-Walled Carbon Nanotubes with High CO Tolerance for Methanol Electrooxidation.

Anode catalysts are important for direct methanol fuel cells (DMFCs) of energy conversion. Herein, we report a novel strategy by ethylene glycol-based deep eutectic solvents (EG-DESs) for the fabrication of a multi-walled carbon nanotubes (MWCNTs)-supported Pt nanoparticles catalyst (referred to as Pt/CNTs-EG-DES). The Pt/CNTs-EG-DES catalyst provides an increased electrochemically active surface area (ECSA) and shows remarkably improved electrocatalytic performance towards methanol oxidation reaction compared to Pt/CNTs-W (fabricated in water) and commercial Pt/C catalysts. The improved performance is attributed to the generation of more Pt-O bonds which change the electronic states of the Pt atoms and the special node structure that obtains more active sites for a high CO resistance. This study suggests an effective synthesis strategy for Pt-based electrocatalysts with high performance for DMFC applications.

Growth Modulation of High-Entropy Alloys for Electrocatalytic Methanol Oxidation Reaction.

High-entropy alloy (HEA) electrocatalysts have exhibited remarkable catalytic performance because of their synergistic interactions among multiple metals. However, the growth mechanism of HEAs remains elusive, primarily due to the constraints imposed by the current synthesis methodologies for HEAs. In this work, an innovative electrodeposition method was developed to fabricate Pt-based nanocomposites (Pt1Bi2Co1Cu1Ni1/CC), comprising HEA nanosheets and carbon cloths (CCs). The reaction system could be effectively monitored by taking samples out from the system during the reaction process, facilitating in-depth insight into the growth mechanism underlying the material formation. In particular, Pt1Bi2Co1Cu1Ni1/CC nanocomposites show superior methanol oxidation reaction (MOR) performance (mass activity up to 5.02 A mgPt-1). Upon structural analysis, the d-band center of Pt1Bi2Co1Cu1Ni1/CC is lower in comparison with that of Pt1Bi2/CC and Pt/CC, demonstrating the formation of a rich-electron structure. Both the uniformity of HEAs and the carbon-supported effect could provide additional active sites. These findings suggest that the strong electronic interaction within HEAs and additional active sites can effectively modulate the catalytic structure of Pt, which benefits the enhanced CO tolerance and MOR performance.

Mo-modified Pt/C electrocatalyst prepared by the catalytic decomposition of molybdenum peroxo-complexes for the hydrogen oxidation reaction with enhanced CO tolerance

Commercial 20 % Pt/C catalyst was modified by molybdenum via catalytic decomposition of peroxocomplexes of molybdenum with the subsequent reduction of the Pt2Mo1/C precursor in H2 flow at 600 °C. The detailed HRTEM, EDX, XRD and XPS studies showed that amorphous molybdenum oxide was deposited on Pt particles surface and partially on carbon support. After reduction of the Pt2Mo1/C precursor, the substantial Mo fraction merges the structure of Pt particles thus forming PtMo alloy with reduced lattice parameter, while the rest of molybdenum covers the surface of PtMo particles as MoO3. The presented method of Mo-modification of Pt-based catalysts provides rather simple way to vary Pt:Mo molar ratio. Electrochemical study revealed that the amount of the surface MoO3 plays a key role in the CO tolerance of the PtMo/C catalyst. As prepared Pt2Mo1/C precursor is 15 times superior to the Pt/C catalyst in the CO-tolerance. After reduction, the Pt2Mo1/C electrocatalyst exhibits extremely high CO-tolerance, more than 100 times higher than that of the pristine commercial platinum catalyst.

Breaking the Trade-Off between CO Tolerance and Intrinsic Activity in Hydrogenation on Metal Oxide-Supported Noble Metal Single Atoms through Coordination Environment Engineering

Breaking the Trade-Off between CO Tolerance and Intrinsic Activity in Hydrogenation on Metal Oxide-Supported Noble Metal Single Atoms through Coordination Environment Engineering

Halogen Tailoring of Platinum Electrocatalyst with High CO Tolerance for Methanol Oxidation Reaction.

The catalytic activity of platinum for CO oxidation depends on the interaction of electron donation and back-donation at the platinum center. Here we demonstrate that the platinum bromine nanoparticles with electron-rich properties on bromine bonded with sp-C in graphdiyne (PtBr NPs/Br-GDY), which is formed by bromine ligand and constitutes an electrocatalyst with a high CO-resistant for methanol oxidation reaction (MOR). The catalyst showed peak mass activity for MOR as high as 10.4 A mgPt -1, which is 20.8 times higher than the 20 % Pt/C. The catalyst also showed robust long-term stability with slight current density decay after 100 hours at 35 mA cm-2. Structural characterization, experimental, and theoretical studies show that the electron donation from bromine makes the surface of platinum catalysts highly electron-rich, and can strengthen the adsorption of CO as well as enhance π back-donation of Pt to weaken the C-O bond to facilitate CO electrooxidation and enhance catalytic performance during MOR. The results highlight the importance of electron-rich structure among active sites in Pt-halogen catalysts and provide detailed insights into the new mechanism of CO electrooxidation to overcome CO poisoning at the Pt center on an orbital level.

RhCo alloyed nanodendrites as an efficient electrocatalyst for boosting electro oxidation of ethylene glycol in alkaline media

Since Pt- and Pd-based catalysts, as the most common anode catalysts, usually suffer from CO poisoning issue during the electro oxidation of ethylene glycol, it is essential to explore more high-efficiency Pt- and Pd-free ethylene glycol oxidation reaction (EGOR) catalysts for better service in direct ethylene glycol fuel cells (DEGFCs). In this work, RhCo alloyed nanodendritic catalysts applied on EGOR in alkaline solution are designed and synthesized by a solvothermal method. The RhCo nanodendrites consist of radially distributed pine tree shaped flakes and rod-like crystals. The mass activity for the as-prepared Rh3Co1 nanodendrites during the EGOR reaches up to 3018.7 mA mg−1, which is 2.2-folds higher than that of commercial Pt/C. Moreover, the Rh3Co1 nanodendrites exhibit better stability and CO tolerance toward the EGOR than pure Rh nanodendrites and commercial Pt/C. Experimental observations in combination with density functional theory (DFT) calculations reveal that the notably promoted catalytic performances of Rh3Co1 nanodendrites are mainly attributed to the distinct nanodendritic morphology and the synergistic effect of Rh and Co. This work provides a valuable insight for developing efficient electrocatalysts for DEGFCs.

Strengthening the activity and CO tolerance with bi-component PtNi/NbN-C catalyst for methanol alkaline electrooxidation

It is critical to create the anodic catalysts with high efficiency and economy for direct methanol fuel cells (DMFCs). Here, a series of PtNi/NbN-C catalysts (M=Co, Sn, Ni) are developed using the glycol solvothermal process, to investigate the catalytic effficiency for alkaline methanol oxidation reaction (MOR). Catalytic performance evaluation experiments show that the doped Ni species bring the enhancement effect on Pt/NbN-C for the alkaline MOR. The mass activities of PtxNiy/NbN-C show a volcanic trend with the increased Ni contents. PtNi/NbN-C has the highest mass activity (6025.5 mA·mg-1Pt) for alkaline MOR, 18.3 times greater than that of the Pt/C commercial catalyst. The LSV, EIS, Tafel, CA and CO stripping results imply PtNi/NbN-C also exhibits the lowest onset potential, charge transfer resistance, fastest kinetics, highest CO tolerance and stability. When the XRD, HRTEM, and XPS analysis are combined, it is discovered that the electronic effect between the Pt, Ni, and NbN species is mostly responsible for the catalytic performance enhancement is mainly depend on the electronic effect among the Pt, Ni and NbN species. The presence of Pt in an electron-deficient state can enhance the conversion of adsorbed methanol and intermediates, evidenced by a direct relationship between the d-band centers and the mass activities for MOR of different catalysts. This study may provide guidance for the development of anodic materials for DMFCs.

Electronegativity- induced cobalt-doped platinum hollow nanospheres with high CO tolerance for efficient methanol oxidation reaction

Although Platinum (Pt)-based alloys have garnered significant interest within the realm of direct methanol fuel cells (DMFCs), there still exists a notable dearth in the exploration of the catalytic behavior of the liquid fuels on well-defined active sites and unavoidable Pt poisoning because of the adsorbed CO species (COads). Here, we propose an electronegativity-induced electronic redistribution strategy to optimize the adsorption of crucial intermediates for the methanol oxidation reaction (MOR) by introducing the Co element to form the PtCo alloys. The optimal PtCo hollow nanospheres (HNSs) exhibit excellent high-quality activity of 3.27 A mgPt−1, which is 11.6 times and 13.1 times higher than that of Pt/C and pure Pt, respectively. The in-situ Fourier transform infrared reflection spectroscopy validates that electron redistribution could weak CO adsorption, and subsequently decrease the CO poisoning adjacent the Pt active sites. Theoretical simulations result show that the introduction of Co optimize surface electronic structure and reduce the d-band center of Pt, thus optimized the adsorption behavior of COads. This study not only employs a straightforward method for the preparation of Pt-based alloys but also delineates a pathway toward designing advanced active sites for MOR via electronegativity-induced electronic redistribution.

Ultrathin ternary PtNiRu nanowires for enhanced oxygen reduction and methanol oxidation catalysis via d-band center regulation

Direct methanol fuel cells rely on the efficiency of their anode/cathode electrocatalysts to facilitate the methanol oxidation reaction and oxygen reduction reaction, respectively. Platinum-based nanocatalysts are at the forefront due to their superior catalytic properties. However, the high-cost, scarcity, and low CO tolerance of platinum pose challenges for the scalable application of DMFCs. Herein, we report novel ultrathin ternary PtNiRu alloy nanowires to improve Pt utilization and CO tolerance. These novel electrocatalysts incorporate the oxophilic metal Ru into ultrathin PtNi nanowires, aiming to enhance the intrinsic activity of platinum while leveraging the long-term durability and high utilization efficiency provided by the bimetallic synergistic effect. The PtNiRu NWs significantly enhance both mass activity and specific activity for ORR, performing about 6.9 times and 3.9 times better than commercial Pt/C, respectively. After a rigorous durability test of 10,000 cycles, the PtNiRu NWs only exhibited a 25.2 % loss in mass activity. Additionally, for MOR, the MA and SA of PtNiRu NWs exceed that of Pt/C catalyst by 4.30 and 2.72 times, respectively, and exhibit exceptional resistance to CO poisoning. Theoretical insights from density functional theory calculations suggest that the introduction of Ru modulates the d-band center of the surface Pt atoms, which contributes to decreased binding strength of oxygenated species and an elevated dissolution potential, substantiating the enhanced performance metrics, and the durability enhancement stems from the stronger PtM bonds than those in PtNiRu NWs resulted from PtRu covalent interactions. These findings not only provide a new perspective on platinum-based nanocatalysts but also significantly advance the quest for more efficient and durable electrocatalysts for DMFCs, representing a substantial stride in fuel cell technology.

Pt-Ru atomic alloys confined in mesoporous carbon hollow spheres for accelerating methanol oxidation

Active and durable electrocatalysts are essential for commercializing direct methanol fuel cells. However, Pt-based catalysts, extensively utilized in the methanol oxidation reaction (MOR), are suffered from resource scarcity and CO poisoning, which degrade MOR activity severely. Herein, Pt1Rux bimetallic catalysts were synthesized by confining Pt1Rux alloys within the shells of mesoporous carbon hollow spheres (MCHS) via a vacuum-assisted impregnation method (Pt1Rux@MCHS). The confinement effect induced by mesoporous carbon hollow spheres resulted in a robust structure of Pt1Ru3@MCHS with an ultrafine dispersion of alloy nanoparticles. The experimental and theoretical results confirmed that the boosting electrocatalytic activity and stability of the MOR over Pt1Ru3@MCHS were contributed to the regulated electronic structure as well as the superior CO tolerance of atomic Pt site caused by the electronic interaction between single Pt atoms and Ru nanoparticles. This strategy is versatile for the rational design of Pt-based bimetallic catalysts and has a positive impact on MOR performance.

Electrodeposited Pt nanoparticles loaded on support composites of metal-organic frameworks and carbon quantum dots for the enhancement of alcohol electrooxidation

Metal-organic frameworks comprising divalent metal (M)-linked 4,4′-bipyridine (bpy), {[CuII4(bpy)3(OH)2(mal)3]·4H2O}n(Cubpy) and Ni2(bpy)3(NO3)4(H2O)4(Nibpy) were modified with carbon quantum dots (Mbpy/CQD; M = Cu, Ni) to prepare a composite support. Then, platinum (Pt) nanoparticles were electrodeposited onto the modified Mbpy/CQD support for the preparation of Pt-based catalysts (Pt/Mbpy/CQD) for the electrocatalytic improvement of alcohol oxidation. The influence of Mbpy with electrodeposited Pt nanostructures on CQD support electrodes is particularly discussed in detail through numerous physical characterizations, e.g., SEM, TEM, EDX, XPS, XRD, and elemental mapping. Dispersed Pt nanoparticles with diameters of 3-10 nm can be obtained on the modified Mbpy/CQD supports with suitable chemical and structural conditions for electrocatalytic oxidation improvement. The various prepared Pt/Mbpy/CQD catalysts with different compositions also enhance the kinetics of alcohol oxidation; they have a greater electrochemically active surface area (ECSA) and more development activity for alcohol oxidation than do the Pt/CQD catalysts. For the oxidation of all the selected small alcohol molecules, e.g., methanol, ethanol and isopropanol, the Pt/Cubpy/CQD catalyst composites also mostly exhibited improved catalytic activity, outstanding stability, and lower onset potential (Eonset) and CO tolerance. The favorable performance of the prepared composite catalysts is attributed to their superior ECSA owing to the suitable mixed surface of metal and functional groups of electrodeposited Pt, Mbpy, and CQD on the catalytic composites. Consequently, these as-prepared Pt/Mbpy/CQD composites, which are promising oxidative heterogeneous catalysts, can be used as active and stable catalysts for alcohol oxidation in alkaline solutions.

Non-metal doping enhsances oxygen reduction kinetics and CO2 tolerance of SrFeO3-δ perovskite as high-performance cathodes for solid oxide fuel cells

The sluggish of the oxygen reduction reaction (ORR) kinetics and the susceptibility to CO2 interactions are major barriers to the widespread application of solid oxide fuel cells (SOFCs). In this study, a non-metal cation doping strategy was employed to enhance the ORR catalytic activity and CO2 tolerance of SrFeO3-δ cathode. SrFe1-xPxO3-δ (SFPx, x = 0, 0.05, 0.1, 0.15, 0.2) materials were synthesized by substituting phosphorus (P) for Fe in SrFeO3-δ. The doping of P facilitated the formation of oxygen vacancies in SrFeO3-δ, enhancing oxygen adsorption, dissociation, diffusion, and charge transfer processes, leading to a notable increase in ORR catalytic activity. At 800 ℃, the polarization resistance of SFP0.15 was 0.08 Ω cm2, a reduction of 42.86 % compared to undoped SrFeO3-δ. Additionally, SFP0.15 achieved a peak power density of 749.36 mW cm2, representing a 91.99 % enhancement over SrFeO3-δ. These findings suggest that non-metal cation doping is an effective approach to boost the performance of SrFeO3-δ perovskite cathode.

Hexa‐atom Pt Catalyst Fabricated by a Ligand Engineering Strategy for Efficient Hydrogen Oxidation Reaction

AbstractAtomically precise supported nanocluster catalysts (APSNCs), which feature exact atomic composition, well‐defined structures, and unique catalytic properties, offer an exceptional platform for understanding the structure‐performance relationship at the atomic level. However, fabricating APSNCs with precisely controlled and uniform metal atom numbers, as well as maintaining a stable structure, remains a significant challenge due to uncontrollable dispersion and easy aggregation during synthetic and catalytic processes. Herein, we developed an effective ligand engineering strategy to construct a Pt6 nanocluster catalyst stabilized on oxidized carbon nanotubes (Pt6/OCNT). The structural analysis revealed that Pt6 nanoclusters in Pt6/OCNT were fully exposed and exhibited a planar structure. Furthermore, the obtained Pt6/OCNT exhibited outstanding acidic HOR performances with a high mass activity of 18.37 A ⋅ mgpt−1 along with excellent stability during a 24 h constant operation and good CO tolerance, surpassing those of the commercial Pt/C. Density functional theory (DFT) calculations demonstrated that the unique geometric and electronic structures of Pt6 nanoclusters on OCNT altered the hydrogen adsorption energies on catalytic sites and thus lowered the HOR theoretical overpotential. This work presents a new prospect for designing and synthesizing advanced APSNCs for efficient energy electrocatalysis.

Hexa-atom Pt Catalyst Fabricated by a Ligand Engineering Strategy for Efficient Hydrogen Oxidation Reaction.

Atomically precise supported nanocluster catalysts (APSNCs), which feature exact atomic composition, well-defined structures, and unique catalytic properties, offer an exceptional platform for understanding the structure-performance relationship at the atomic level. However, fabricating APSNCs with precisely controlled and uniform metal atom numbers, as well as maintaining a stable structure, remains a significant challenge due to uncontrollable dispersion and easy aggregation during synthetic and catalytic processes. Herein, we developed an effective ligand engineering strategy to construct a Pt6 nanocluster catalyst stabilized on oxidized carbon nanotubes (Pt6/OCNT). The structural analysis revealed that Pt6 nanoclusters in Pt6/OCNT were fully exposed and exhibited a planar structure. Furthermore, the obtained Pt6/OCNT exhibited outstanding acidic HOR performances with a high mass activity of 18.37 A ⋅ mgpt -1 along with excellent stability during a 24 h constant operation and good CO tolerance, surpassing those of the commercial Pt/C. Density functional theory (DFT) calculations demonstrated that the unique geometric and electronic structures of Pt6 nanoclusters on OCNT altered the hydrogen adsorption energies on catalytic sites and thus lowered the HOR theoretical overpotential. This work presents a new prospect for designing and synthesizing advanced APSNCs for efficient energy electrocatalysis.

Rapid oxygen atom capture on perovskite surface boosting the activity and durability of cathode for solid oxide fuel cells

The content and distribution of surface oxygen vacancies are crucial for the oxygen reduction reaction (ORR) activity of solid oxide fuel cell (SOFC) cathodes. Therefore, a facile and rapid oxygen atom capture strategy is developed to modulate the surface oxygen vacancies of the cathode. By controlling the duration of NaBH4 solution reduction, precise modulation of the surface oxygen vacancies of NdBa0.5Sr0.5Co2O5+δ (NBSC) is achieved. Consequently, the processes of oxygen adsorption, dissociation, and diffusion on the surface of the NBSC cathode are enhanced. The research findings demonstrate that NBSC reduced for 10 min (RE-NBSC-10) exhibits optimal ORR catalytic activity and CO2 tolerance. At 800 °C, the Rp of RE-NBSC-10 decreases by 45 %, reaching 0.006 Ω‧cm2. Moreover, the maximum power density (MPD) of the RE-NBSC-10 cathode reaches 1.16 W cm−2, representing a 90.2 % improvement compared to NBSC. This research provides an efficient approach for the advancement of materials tailored for next-generation energy conversion devices.

Studying Ru Dissolution in Pt, Ru, and Pd Core-Shell Nanostructures As a Function of Stress Test Coupled with CO Stripping Analyses

Hydrogen gas contaminated with CO, when used as a reactant on the fuel cell anode, has a detrimental impact on its performance. A low CO contamination of 5 ppm can decrease the fuel cell power density to less than half the value obtained with pure H2.1 To combat CO poisoning of the anode, PtRu/C is currently used on the fuel cell anode instead of the nominally more active Pt/C catalyst. The PtRu/C catalyst reduces CO poisoning by oxidizing this adsorbate within the potential range of hydrogen oxidation. The addition of a third metal such as Pd, Sn, or Co to this bimetallic alloy has demonstrated further improvements to the CO tolerance of the catalyst. The wide application of these alloys is, however, restricted due to the instability of non-noble metal, Ru, at high potentials experienced during fuel cell startup, shutdown, and fuel starvation conditions.2 Dissolution of Ru leads to structural modifications to the nanocatalyst and, thus, directly impacts the CO tolerance of the catalyst because of its structure-property relationship. The dissolution of Ru not only decreases the CO tolerance of the anode, but also reduces the oxygen reduction activity of the cathode due to Ru migration, causing an overall decline in fuel cell performance.3 These structural changes result in a complex heterogeneous particle surface with varying amounts of Pt atoms on each catalytic site, as observed at the atomic level using TEM imaging techniques. The use of TEM does, however, require a visual inspection of the sample. Thus, obtaining results based on TEM analysis alone is not only time-consuming but can also be subjective.4 Studying the structural changes of an ensemble of nanoparticles using a series of electrochemical techniques can help to better understand the degradation mechanism(s) of a catalyst. In this work, modifications to the structure of an ensemble of nanocatalysts because of Ru dissolution during stress tests were evaluated by conducting CO stripping analyses after a well-defined period of testing.Nanoparticles of Pd@PtRu, PtRu@Pd, and PdRu@Pt (core@shell) structures along with a PtRuPd alloy were prepared using a water-in-oil microemulsion synthesis method and examined for their structural stability. These nanoparticles were each adsorbed onto separate carbon supports. The successful formation of an alloy or core-shell structure was assessed by electron diffraction and X-ray spectroscopy techniques. The process of alloying metals and creating core-shell structures can alter the electronic structure of a material, which was studied using X-ray photoelectron spectroscopy. Given the applicability of these catalysts to the anode of the fuel cell, hydrogen oxidation activity was investigated using rotating disk electrode studies, while CO tolerance was assessed using CO stripping analysis. Their structural durability was tested by cycling the applied potential between 0.6 to 0.95 V (vs RHE) for 5000 complete cycles while immersing the electrocatalyst in 0.5 M H2SO4. Changes in the position and shape of the CO oxidation peak were analysed after 200, 500, 1000, 3000 and 5000 cycles to gain insights into the structural modifications occurring to each catalyst throughout these stress tests. The results provide insights into the structural changes and the processes of these modifications that take place during these tests. These studies also suggest an optimum structural configuration of Pt, Ru, and Pd metals among the tested alloys and nanostructures to provide a relatively high degree of structural stability while maintaining tolerance to CO poisoning. This type of comparative analysis can also be utilized in guiding the optimization of additional nanocatalysts for other electrocatalytic reactions. References H.-F. Oetjen, V. M. Schmidt, U. Stimming and F. Trila, J. Electrochem. Soc., 143, 3838 (1996).E. Antolini, J. Solid State Electrochem., 15, 455–472 (2011).L. Gancs, B. N. Hult, N. Hakim and S. Mukerjee, Electrochem. Solid-State Lett., 10, B150 (2007).A. Hrnjic et al., Electrochim. Acta, 388, 138513 (2021).