High-performance Electrocatalysts For Oxygen Reduction Reaction Research Articles

Au enables PdAu aerogel efficient catalysts for oxygen reduction and C2 alcohol oxidation

Metallic aerogels (MAs) with self-supporting three-dimensional (3D) porous structures constitute a potential platform for the construction of robust catalysts. In this work, we successfully constructed 3D PdAu MAs with the optimized d-band electron of Pd and geometrical lattice expansion using a maneuverable in-situ seed-mediated strategy at room temperature. The introduction of Au accelerated the kinetics of Pd4Au3 MAs toward oxygen reduction reaction (ORR), ethylene glycol oxidation reaction (EGOR), and ethanol oxidation reaction (EOR) in alkaline electrolyte, boosting the activity and stability of Pd4Au3 MAs. The mass activities of Pd4Au3 MAs/C in ORR, EGOR and EOR were 1.74, 8.57, and 9.54 A mgPd−1, respectively, which were remarkably better than those of referenced Pd MAs/C, commercial Pt/C and Pd/C. The rotating ring-disk electrode measurement illustrated that Pd4Au3 MAs/C achieved a 4-electron transfer process in ORR from O2 to OH−. In-situ Fourier transform infrared spectroscopy revealed that Pd4Au3 MAs/C enabled the cleavage of the C–C bonds, thus accomplishing the C1-complete oxidation of 10-electron ethylene glycol and 12-electron ethanol. This study provides an efficient strategy to fabricate binary non-Pt alloy aerogels as high-performance multifunctional electrocatalysts for ORR, EGOR, and EOR.

Upcycling retired Li-ion batteries into high-performance oxygen reduction reaction electrocatalysts in flexible Al-air batteries

Upcycling retired lithium-ion batteries (LIBs) into value-added electrocatalysts represents a promising strategy for tuning the trash into treasure. Herein, an effective approach is reported to convert the LIB anode residues into electrocatalysts that enhance the oxygen reduction reaction (ORR). The residues are utilized for synthesizing reduced graphene oxides (rGO) with Mn nanoparticles anchored by N and S dopants (Mn/NS-rGO). A Pt/C-comparable ORR performance is achieved in alkaline media, with the onset and half-wave potentials of 1.01 and 0.87 V, as well as the excellent durability. Density functional theory (DFT) calculations reveal that Mn sites, coordinating with N and S dopants, simultaneously optimize the intermediate adsorption and charge distribution, which in turn facilitates ORR. The solid-state Al-air batteries are assembled by using Mn/NS-rGO as the cathode catalyst, showing the power density of 103.8 mW cm−2, which successfully charge a cell phone and power LED lights under flexible working conditions.

Boron-alloyed porous network platinum nanospheres for efficient oxygen reduction in proton exchange membrane fuel cells

Alloying (or doping) non-metals with platinum (Pt) is an advanced solution for the development of high-performance Pt-based electrocatalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Herein, we report boron (B)-alloyed Pt nanospheres (B-PtNSs) with a porous network nanostructure by a combination strategy of confinement reduction and post-boronation. B-alloying can induce effective electronic/geometric structures, strong Pt-B coordination, and lowered d-band center to weaken the binding energy of oxygenated intermediates on the Pt surface. The H2-O2 PEMFC with such a B-PtNSs/C as the cathode catalyst can reach a maximum power density of 1.49 W cm−2, about 1.28 times higher than that of Pt/C. After 30,000 voltage cycles in the range of 0.6 ∼ 0.95 V, only a 14.1 % loss of initial peak power density can be observed, while that with Pt/C declines 45.7 %. Non-metals alloying with Pt-based nanostructures can enable high-performance ORR electrocatalysts for their practical application in PEMFCs.

Design strategies towards transition metal single atom catalysts for the oxygen reduction reaction – A review

The electrochemical oxygen reduction reaction (ORR) is pivotal in energy conversion <i>via</i> a 4e⁻ ORR pathway and green hydrogen peroxide production <i>via</i> 2e⁻ ORR pathway. Transition metal single atom catalysts (TM SACs) have attracted intense attention in recent years for ORR due to their high activity and near maximum metal atom utilization. The future development of TM SACs for ORR requires improved understanding of reaction pathways, since currently the true origin of activity remains contentious owing to the lack of qualitative/quantitative information about active sites. Knowledge-guided design is imperative for the optimization of TM SACs performance in terms of activity and selectivity. This review focuses on the latest progress in the design of TM SACs for ORR, placing particular attention on efforts to elucidate reaction mechanisms. Experimental evidence based on <i>in-situ/operando</i> characterization measurements, along with theoretical predictions, are summarized to deepen understanding of the structure-performance relationships at both atomic and molecular level. Finally, some perspectives are offered relating to the fundamental science needed for TM SACs to find practical application in energy storage and conversion devices. We hope this review will inspire the development of new synthetic routes towards high-performance ORR electrocatalysts for the energy sector.

TiO/Ti3O5-Decorated Electrospun Carbon Nanofibers as High-Performance Oxygen Reduction Reaction Electrocatalysts

TiO/Ti₃O₅-Decorated Electrospun Carbon Nanofibers as High-Performance Oxygen Reduction Reaction Electrocatalysts

N and S dual-coordinated Fe single-atoms in hierarchically porous hollow nanocarbon for efficient oxygen reduction

Fe-, and N-co-doped carbon (FeNC) electrocatalysts are promising alternatives to Pt-based catalysts for oxygen reduction reaction (ORR); however, simultaneously enhancing their intrinsic activity and exposure of Fe active sites remains challenging. Herein, we report S-modified Fe single-atom catalysts (SACs) anchored on N,S-co-doped hollow porous nanocarbon (Fe/NS-C) for ORR. The unique hollow structure and large surface area of the SACs are favorable for mass/electron transport and exposure of Fe single-atom active sites. The as-prepared Fe/NS-C electrocatalysts display a high-efficiency ORR activity with a half-wave potential of 0.893 V versus the reversible hydrogen electrode and exceed that of the benchmark commercial Pt/C catalyst as well as most reported transition-metal based SACs. Impressively, the Fe/NS-C-based Al-air battery (AAB) displays a high open circuit voltage of 1.48 V, a maximum power density of 140.16 mW cm−2, and satisfactory durability, outperforming commercial Pt/C-based AAB. Furthermore, Fe/NS-C exhibits considerable potential as a cathode catalyst for application in direct methanol fuel cells. Experimental and theoretical calculation results reveal that the excellent ORR performance of Fe/NS-C can be contributed to the highly active FeN3S sites and the unique hollow structure. This work provides new insights into the rational design and synthesis high-performance ORR electrocatalysts for energy conversion and storage devices. of employing ZIF-8 as precursors.

Soft‐Pyrolysis Co–N‐Implanted Polymer to Gain High‐Density Co–Nx Sites on Carbons for Efficient Oxygen Reduction in Zn–Air Batteries

A soft‐pyrolysis strategy by heating Co–N‐implanted covalent organic polymer combining on carbon nanotubes at ≤500 °C has been developed to obtain efficient Co–N–C electrocatalysts for oxygen reduction reaction (ORR). The prepared Co–N–C is highly active for ORR with a half‐wave potential of 0.91 V versus RHE in 0.1 m KOH electrolyte, superior to most of previously reported Co‐based electrocatalysts. When employing it as cathode electrocatalyst, the homemade Zn–air battery shows a peak power density of 304.2 mW cm−2, comparable to the parallel power density (250 mW cm−2) of Zn–air battery with Pt/C (20 wt%) electrocatalyst at cathode. The soft‐pyrolysis strategy not only helps to generate high density Co–Nx active sites on carbons but also facilitates the optimizing balance between active site densities, graphitization degree, and pore structure of Co–N–C catalysts. Herein, a simple and energy‐effective low‐temperature pyrolysis strategy to obtain high‐performance ORR electrocatalyst is provided.

Three-dimensional porous nitrogen-doped carbon nanosheets with ultra-high surface area for high-performance oxygen reduction reaction electrocatalysts

A series of three-dimensional (3D) porous nitrogen-doped carbon nanosheets (PNCNs) have been successfully fabricated via a high-pressure carbonization followed by high-temperature thermal treatment. With the prolonging of thermal treatment time, the 3D PNCNs demonstrate several remarkable advantages for oxygen reduction reaction (ORR) electrocatalysts, including ultra-high specific surface area (more than 2100 m2/g−1), unique 3D porous structure, abundant defects, and suitable configuration of nitrogen. With these merits, the N-C-2 h based electrocatalyst exhibits outstanding ORR activities with a comparable onset potential of −40 mV (vs. Ag/AgCl), half-wave potential of −120 mV (vs. Ag/AgCl), satisfactory electron transfer number (4) and superior stability to those of commercial 20% Pt/C. The excellent electrochemical behaviors of 3D PNCNs are confirmed to be dominated by structural characteristics, which can be optimized by varying thermal treatment time. Our work offers a promising way for controllably constructing carbon-based materials with optimized ORR performance.

Molecular Design of Porous Organic Polymer-Derived Carbonaceous Electrocatalysts for Pinpointing Active Sites in Oxygen Reduction Reaction.

The widespread application of fuel cells is hampered by the sluggish kinetics of the oxygen reduction reaction (ORR), which traditionally necessitates the use of high-cost platinum group metal catalysts. The indispensability of these metal catalysts stems from their ability to overcome kinetic barriers, but their high cost and scarcity necessitate alternative strategies. In this context, porous organic polymers (POPs), which are built up from the molecular level, are emerging as promising precursors to produce carbonaceous catalysts owning to their cost-effectiveness, high electrical conductivity, abundant active sites and extensive surface area accessibility. To enhance the intrinsic ORR activity and optimize the performance of these electrocatalysts, recognizing, designing, and increasing the density of active sites are identified as three crucial steps. These steps, which form the core of our review, serve to elucidate the link between the material structure design and ORR performance evaluation, thereby providing valuable insights for ongoing research in the field. Leveraging the precision of polymer skeletons based on molecular units, POP-derived carbonaceous catalysts provide an excellent platform for in-depth exploration of the role and working mechanism for the specific active site during the ORR process. In this review, the recent advances pertaining to the synthesis techniques and electrochemical functions of various types of active sites, pinpointed from POPs, are systematically summarized, including heteroatoms, surficial substituents and edge/defects. Notably, the structure-property relationship, between these active sites and ORR performance, are discussed and emphasized, which creates guidelines to shed light on the design of high-performance ORR electrocatalysts.

Engineering carbon semi-tubes supported platinum catalyst for efficient oxygen reduction electrocatalysis

Innovation of catalyst structure is extremely important to develop the high-performance electrocatalysts for oxygen-reduction reaction (ORR). Herein, nitrogen-doped carbon semi-tube (N-CST) is used as a functional support for stabilizing the microwave-reduced Pt nanoparticles with an average size of ∼2.8nm to synthesize the semi-tubular Pt/N-CST catalyst. The contribution of interfacial Pt-N bond between N-CST support and Pt nanoparticles with electrons transfer from N-CST support to Pt nanoparticles is found by electron paramagnetic resonance (EPR) and X-ray absorption fine structure (XAFS) spectroscopy. This bridged Pt-N coordination can simultaneously help ORR electrocatalysis and promote electrochemical stability. As a result, the innovative Pt/N-CST catalyst exhibits excellent catalytic performance, realizing ORR activity and electrochemical stability superior to the commercial Pt/C catalyst. Furthermore, density functional theoretical (DFT) calculations suggest that the interfacial Pt-N-C site with unique affinity of O∗+ OH∗ can provide new active routes for the enhanced electrocatalytic ORR capacity.

Catalytic upcycling of waste polypropylene for gram-scale production of FeCo@N-doped carbon nanotubes toward efficient oxygen reduction electrocatalysis

Exploring novel low-cost and high-efficiency non-precious metal catalysts for use in oxygen reduction reactions (ORR) is of key importance. Based on catalytic pyrolysis of waste plastics, a facile method for preparing N-doped Fe/Co-encapsulated carbon nanotubes (FexCoy@NCNTs) was proposed. Particularly, gram-scale yield of the composite catalyst (3.87 g) was achieved in one pot with considerable atomic conversion rate of carbon (∼57.3 %) from waste polypropylene to high-quality CNTs, suggesting great potential for waste plastics valorization. The effects of Fe-to-Co ratios were studied by testing the ORR performance of each sample, indicating that as the Fe proportion increased, the ORR performance initially increased and then decreased. The Fe1Co1@NCNTs catalyst showed optimal performance which was comparable with commercial Pt/C catalyst: Particularly, an initial potential of 0.97 V vs RHE, a half-wave potential of 0.81 V vs RHE, and a limiting current density of –5.68 mA cm−2 were recorded. The encapsulated Fe and Co species in N-doped CNTs enhanced catalytic activity, while the porous carbon structure augmented the exposure of active sites. This strategy offers an auspicious platform for reusing waste plastics in the mass production of CNTs, and also provides an innovative approach for preparing low-cost, high-performance, and non-precious metal-based electrocatalysts for ORRs.

N-doping carbon-coated Cu@C(N) nanocapsules synthesized by arc plasma toward high-performance ORR electrocatalyst

The development of efficient and cost-effective methods for the synthesis of non-precious metal as the catalytic material for oxygen reduction reaction (ORR) is addressing a key barrier to fuel cell deployment in a wide range of applications. In this study, core-shell carbon-coated copper nanoparticles (Cu@C) were prepared using arc discharge plasma under argon and hydrogen atmospheres. And nitrogen doping was achieved during the subsequent heat treatment using dicyandiamide as the nitrogen source. The results showed that the catalysts had better ORR catalytic activity, better stability and better methanol tolerance than Pt/C, and the ORR reaction process was nearly four-electron pathway. The successful doping of nitrogen increased the reaction sites. And the addition of copper core improved the conductivity of the catalytic material. Meanwhile, the N-C shell layer protected the Cu nanoparticles from dissolving in aqueous solutions or being chemically oxidized, facilitating the electronic interaction of the core Cu nanoparticles with the N-C shell layer. This study provides an insight into the preparation of high-efficiency non-precious metal-based ORR electrocatalysts by DC arc plasma, a beneficial method.

Dispersed cobalt nanoparticles in the nitrogen doped carbon black as efficient catalysts for oxygen reduction reaction and Zinc-Air batteries

Developing an effective and durable Pt-free oxygen reduction reaction (ORR) catalyst for Zinc-Air batteries (ZABs) is propitious to easing the energy and pollution crisis. Herein, we have prepared Co nanoparticles/N-doped carbon (Co/N/C) with tunable Co contents by the pyrolysis of polydopamine-coated cobalt phthalocyanine/carbon black precursors. Benefiting from the well-dispersed Co nanoparticles and the formation of various active sites (i.e. pyridinic, graphitic N and Co-Nx), the resulting Co/N/C-2.86 wt% catalysts possess a half-wave potential of 0.84 V and a mass activity of 5.18 A/g, illustrating the superior ORR performance. Noteworthy, the ZABs with the cathode of Co/N/C-2.86 wt% display an outstanding cell performance with a large open-circuit voltage (1.542 V), a high specific discharge capacity (744 mAh g−1) and an excellent maximum power density (236 mW cm−2). This work offers a promising approach to rationally design and fabricate high-performance ORR electrocatalysts for advanced ZABs.

Plasma-engineered cobalt nanoparticle encapsulated N-doped graphene nanoplatelets as high-performance oxygen reduction reaction electrocatalysts for aluminum–air batteries

The increasing demand for continuous and eco-friendly alternative energy has prompted interest in aluminum–air (Al–air) batteries owing to their high energy density and safety. On the other hand, the sluggish oxygen reduction reaction (ORR) rate in alkaline electrolytes, which adversely affects the efficiency of the Al–air battery, is still a challenge. A transition metal electrocatalyst consisting of cobalt nanoparticles encapsulated with N-doped graphene nanoplatelets (Co@N/GNP) was synthesized by plasma engineering. In this design, the active Co nanoparticle acted as the ORR active site and the core-shell structure of dominant pyridinic-N graphene led to outstanding catalytic performance (E1/2 = 0.87 V, Eonset = 0.98 V) in an alkaline electrolyte. Furthermore, when applied as a cathode catalyst in practical Al–air batteries, Co@N/GNP showed excellent performance with a peak power density of 143 mW cm-2.

Ordered mesoporous carbon fiber bundles with high-density and accessible Fe-NX active sites as efficient ORR catalysts for Zn-air batteries

Fe-NX/C electrocatalysts have aroused extensive interest in accelerating sluggish oxygen reduction reaction (ORR) kinetics as potential alternatives to platinum catalysts in rechargeable Zn-air batteries (ZABs). However, the low density and poor accessibility of Fe-NX sites have severely restricted the electrocatalytic performance of Fe-NX/C. Herein, Fe, N co-doped ordered mesoporous carbon fiber bundles are prepared through a ligand-assisted strategy with nitrogen-rich 1,10-phenanthroline as space isolation agent. 1,10-Phenanthroline reveals a six-membered heterocyclic structure containing abundant nitrogen species to tightly coordinate with Fe ions, which is conducive to achieving high-density Fe-NX sites. Meanwhile, the adoption of SBA-15 as hard-templates enables the catalysts with highly ordered channels and large specific surface areas, improving the accessibility of Fe-NX sites. The optimal catalyst (PDA-Fe-900) demonstrates a positive half-wave potential of 0.84 V (vs. RHE) in alkaline solution, outperforming the commercial Pt/C (0.83 V). In addition, PDA-Fe-900 delivers comparable ORR performance to commercial Pt/C in acidic electrolyte. Impressively, when PDA-Fe-900 is employed as an air cathode, it achieves large power densities of 163.0 mW/cm2 in liquid-state ZAB and 116.6 mW/cm2 in the flexible solid-state ZAB. This work provides an efficient ligand-assisted pathway for fabricating catalysts with dense and accessible Fe-NX sites as high-performance ORR electrocatalysts for ZABs.

Iron phthalocyanine coupled with nickel-iron selenide layered hydroxide derivative as dual-functional oxygen electrocatalyst for rechargeable zinc-air batteries

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for dual-functional non-precious metal electrocatalysts are promising alternatives for Pt/Ru-based materials in rechargeable zinc-air batteries (ZABs). However, how to achieve dual-functional oxygen electrocatalytic activity on single-component catalysts and identify the sites responsible for ORR and OER still face many challenges. Herein, an efficient and stable dual-functional electrocatalyst is fabricated by a two-step hydrothermal method with iron phthalocyanine (FePc) π-π stacking on nickel-iron selenide layered hydroxide derivatives (Se/Ni3Se4/Fe3O4). The as-prepared multi-component catalyst (named as FePc/Se@NiFe) exhibits better oxygen electrocatalytic properties than Pt/Ru-based catalysts, with a half-wave potential (E1/2) of 0.90 V and an overpotential of 10 mA cm-2 (Ej10) of 320 mV. More importantly, chronoamperometry (I-T) and accelerated durability tests (ADT) show the unordinary stability of the catalyst. Both physical characterization and experimental results verify that the Fe-N4 moieties and Ni3Se4 crystalline phase are the main active sites for ORR and OER activities, respectively. The small potential gap (ΔE = Ej10 - E1/2 = 0.622 V) represents superior dual-functional activities of the FePc/Se@NiFe catalyst. Subsequently, the ZABs assembled using FePc/Se@NiFe exhibit excellent performances. This study offers a promising design concept for promoting further development of high-performance ORR and OER electrocatalysts and their application in ZAB.

The rational design of high-performance graphene-based single-atom electrocatalysts for the ORR using machine learning.

In this work, high-performance two-dimensional (2D) graphene-based single-atom electrocatalysts (ZZ/ZA-MNxCy) for the oxygen reduction reaction (ORR) were screened out using machine learning (ML). A model was built for the fast prediction of electrocatalysts and two descriptors valence electron correction (VEc) and degree of construction differences (DC) were proposed to improve the accuracy of the model prediction. Two evaluation criteria, high-performance catalyst retention rate rR and high-performance catalyst occupancy rate rO, were proposed to evaluate the accuracy of ML models in high-performance catalyst screening. The addition of VEc and DC in the model could change the mean absolute error (MAEtest) of the test set, the coefficient of determination (R2test) of the test set, rO, and rR from 0.334 V, 0.683, 0.222, and 0.360 to 0.271 V, 0.774, 0.421, and 0.671, respectively. The partially screened potential high-performance ORR electrocatalysts such as ZZ-CoN4 and ZZ-CoN3C1 were also further investigated using a Density Functional Theory (DFT) method, which confirmed the accuracy of the ML model (MAE = 0.157 V, R2 = 0.821).

2D RhTe Monolayer: A highly efficient electrocatalyst for oxygen reduction reaction

Oxygen reduction reaction (ORR) electrocatalysts with excellent activity and high selectivity toward the efficient four-electron (4e) pathway are very important for the wide application of fuel cells and are worth searching vigorously. In this study, r-RhTe monolayer is identified as a good ORR electrocatalyst from three 2D RhTe configurations with low Rh-loading (i.e., r-RhTe, o-RhTe and h-RhTe) on the basis of the first-principles calculations. For the most energetically stable r-RhTe, two adjacent positively charged Te atoms on the material surface can provide an active site for oxygen dissociation. Coupled with its high stability and intrinsic conductivity, 2D r-RhTe monolayer is confirmed to possess good catalytic activity and high reaction selectivity toward ORR. Moreover, under the ligand effect caused by the substitution of Cr, Mn and Fe, the ORR catalytic activity of r-RhTe monolayer could be effectively enhanced, where very small over-potential was achieved, and even comparable to or lower than the state-of-the-art Pt (111). This shows it has considerably high ORR activity. This work is highly anticipated to provide excellent candidate materials for ORR catalysis, and the related researches based on the Rh-Te materials will provide a new way to design high-performance ORR electrocatalysts to substitute the precious metal Pt-based catalysts.

Origin of the Rarely Reported High Performance of Mn-doped Carbon-based Oxygen Reduction Catalysts.

Recent efforts to develop durable high-performance platinum-group metal (PGM)-free oxygen reduction reaction (ORR) electrocatalysts have focused on Fe- and Co-based molecular and pyrolyzed catalysts. While Mn-based catalysts have advantages of lower toxicity and higher durability, their activity has been generally poor. Nevertheless, several examples of high-performance Mn-based catalysts have been reported. Thus, it is necessary to understand why Mn-based materials much more rarely show high catalytic ORR performance and to determine the factors that can lead to the achievement of such high performance in these rare cases. We have studied the effects of the changes in the macrocycle structure, axial ligand, distance between the active sites, interactions with the dopant N atoms and the presence of an extended carbon network on the ORR catalysis of various Mn-, Fe-, and Co-based systems through the comparison of the adsorption energies of the ORR intermediates. We find that the sensitivity to the local environment changes is the largest for Mn and is the smallest for Co, with Fe between Mn and Co. Our results showed that the strong binding of OH by Mn and the strong sensitivity of the Mn to the modification of its environment necessitate a precise combination of local environment changes to achieve a high onset potential (Vonset ) in Mn-based catalysts. By contrast, the weaker binding of OH by Fe and Co and their weaker sensitivity to local environment changes lead to a wide variety of local environments with favorable catalytic activity (Vonset >0.7 V) for Co- and Fe-based systems. This explains the scarcity of reported Mn-based pyrolyzed catalysts and suggests that precise material synthesis and engineering of the active site can achieve high-performance Mn-based ORR electrocatalysts with high activity and durability.

Fe-Fe3C Functionalized Few-Layer Graphene Sheet Nanocomposites for an Efficient Electrocatalyst of the Oxygen Reduction Reaction.

Preparation of a high-efficiency, low-cost, and environmentally friendly non-precious metal catalyst for the oxygen reduction reaction (ORR) is highly desirable in fuel cells. Herein, a Fe–Fe3C-functionalized few-layer graphene sheet (Fe/Fe3C/FLG) nanocomposite was fabricated through the vacuum heat treatment technique using ferric nitrate and glucose as the precursors and exhibited a high-performance ORR electrocatalyst. Multiple characterizations confirm that the nanosized Fe particles with the Fe3C interface are uniformly distributed in the FLGs. Electrocatalytic kinetics investigation of the nanocomposite indicates that the electron transfer process is a four-electron pathway. The formation of the Fe3C interface between the Fe nanoparticles and FLGs may promote the electron transfer from the Fe to FLGs. Furthermore, the Fe/Fe3C/FLG nanocomposite not only exhibits high ORR catalytic activity but also displays desirable stability. Consequently, the obtained Fe/Fe3C/FLG nanocomposite might be a promising non-precious, cheap, and high-efficiency catalyst for fuel cells.