Lithium-Mediated Ammonia Electrosynthesis with Ether-Based Electrolytes.

Ammonia is of great importance in fertilizer production and chemical synthesis. It can also potentially serve as a carbon-free energy carrier for a future hydrogen economy. Motivated by a worldwide effort to lower carbon emissions, ammonia synthesis by lithium-mediated electrochemical nitrogen reduction (LiNR) has been considered as a promising alternative to the Haber-Bosch process. A significant performance improvement in LiNR has been achieved in recent years by exploration of favorable lithium salt and proton donor for the electrolyte recipe, but the solvent study is still in its infancy. In this work, a systematic investigation on ether-based solvents toward LiNR is conducted. The assessments of solvent candidates are built on their conductivity, parasitic reactions, product distribution, and faradaic efficiency. Notably, dimethoxyethane gives the lowest potential loss among the investigated systems, while tetrahydrofuran achieves an outstanding faradaic efficiency of 58.5 ± 6.1% at an ambient pressure. We found that solvent molecules impact the above characteristics by dictating the solvation configurations of conductive ions and inducing the formation of solid electrolyte interphase with different compositions. This study highlights the importance of solvents in the LiNR process and advances the electrolyte optimization for better performance.

Structural and Transport Properties of Hydrophilic and Hydrophobic Modified Ionomers in Proton Exchange Membrane Fuel Cells.

The sluggish commercial application of proton exchange membrane fuel cells (PEMFCs) with low Pt loading is chiefly hindered by concentration polarization loss, particularly at high current density regions. Addressing this, our study concentrates on the ionomer membranes in the cathode catalyst layer (CCL) and explores the potential of incorporating additional hydrophilic or hydrophobic components to modify these ionomers. Therefore, an all-atom model was constructed and for the ionomer and hydrophilic and hydrophobic modifications were implemented via incorporating SiO2 and PTFE, respectively. The investigation was conducted via molecular dynamics (MD) simulations to predict the morphology and structure of the ionomer and analyze the kinetic properties of oxygen molecules and protons. The simulation results elaborate that the hydrophilic and hydrophobic modifications favor the phase separation and the self-diffusion coefficients of oxygen molecules and protons are enhanced. Considering the hydration level of the ionomer films, hydrophilic modification facilitates mass transfer under low-hydration-level conditions, while hydrophobic modification is more effective in optimizing mass transfer as the hydration level increases. The optimal contents of SiO2 and PTFE for each hydration level in this work are 9.6% and 45%, respectively. This work proposes a reliable model and presents a detailed analysis of hydrophilic and hydrophobic modifications, which provides theoretical guidance for quantitative preparations of various composite membranes.

Crystalline-Amorphous IrOx Supported on Perovskite Nanotubes for pH-Universal OER.

Designing catalysts with desirable oxygen evolution reaction (OER) performance under pH-universal conditions is of great significance to promote the development of hydrogen production. Herein, we successfully synthesized a crystalline-amorphous IrOx supported on perovskite oxide nanotubes to obtain IrOx@La0.6Ca0.4Fe0.8Ni0.2O3 with superior OER performance in whole pH media. The overpotential of the IrOx@La0.6Ca0.4Fe0.8Ni0.2O3 catalyst in media of pH 14, 7.2, and 1 has been demonstrated to be 120, 400, and 143 mV, respectively, with no significant element dissolution as well as double-layer capacitance decay after the durability test. Through comparative experiments with IrOx@CNT and the physical mixture of IrOx and La0.6Ca0.4Fe0.8Ni0.2O3, it is found that the strong metal-support interaction (SMSI) in IrOx@La0.6Ca0.4Fe0.8Ni0.2O3 makes IrOx exist in an amorphous state rich in Ir3+, which is closely associated with the surface-active species Ir-OH. Through the regulation of Ir by a perovskite oxide support at the heterointerface, the reaction breaks through the limitation of the adsorbate evolution mechanism (AEM) and converts to a lattice-oxygen-mediated mechanism (LOM), which was fully demonstrated by the addition of the probe tetramethylammonium cation (TMA+), a LOM reaction intermediate, to the electrolyte. This work fills the research gap of perovskite oxide supported Ir-based catalysts with heterogeneous structures, providing an excellent strategy for the structural design of efficient pH-universal OER catalysts for hydrogen production systems.

A simple control and high accuracy measurement method of open-cell four-electrode conductivity electrode.

The paper presents a simple control and high-accuracy measurement method for a four-electrode conductivity probe based on the principle of the bi-directional voltage pulse. The two-way differential AC (alternating current) pulse voltage signal for the reference resistance and solution resistance is modulated into the single DC stationary voltage response signal to drop the demand for software and hardware and effectively eliminate the influence of excitation voltage pulse amplitude on measurement accuracy, and then the synchronous rectification DC measurement is proposed without any control timing. Meanwhile, the mathematical expression between the single output DC voltage signal and the solution conductivity is given. The test results in the laboratory and in the field indicate that the relative error of the conductivity measurement is within 2.5% in a conductance range of 10 uS/cm to 200 mS/cm, and the proposed measurement method has a good application prospect in application.

Insight into Oxygen Transport in Solid and High-Surface-Area Carbon Supports of Proton Exchange Membrane Fuel Cells.

Understanding the oxygen transport mechanism through an ionomer film that covered the catalyst surface is essential for reducing local oxygen transport resistance and improving the low Pt-loading proton exchange membrane fuel cell performance. Besides the ionomer material, the carbon supports, upon which ionomers and catalyst particles are dispersed, also play a crucial role in local oxygen transport. Increasing attention has been paid to the effects of carbon supports on local transport, but the detailed mechanism is still unclear. Herein, the local oxygen transports based on conventional solid carbon (SC) and high-surface-area carbon (HSC) supports are investigated by molecular dynamics simulations. It is found that oxygen diffuses through the ionomer film that covered the SC supports via "effective diffusion" and "ineffective diffusion". The former denotes the process by which oxygen diffuses directly from the ionomer surface to the Pt upper surface through small and concentrated regions. In contrast, ineffective diffusion suffers more restrictions by both carbon- and Pt-dense layers, and thus, the oxygen pathways are long and tortuous. The HSC supports exhibit larger transport resistance relative to SC supports due to the existence of micropores. Also, the major transport resistance originates from the carbon-dense layer as it inhibits oxygen from diffusing downward and migrating toward the pore opening, while the oxygen transport inside the pore is facile along the pore's inner surface, which leads to a specific and short diffusion pathway. This work provides insight into oxygen transport behavior with SC and HSC supports, which is the basis for the development of high-performance electrodes with low local transport resistance.

Innovative Insight into O2/N2 Permeation Behavior through an Ionomer Film in Cathode Catalyst Layers of Polymer Electrolyte Membrane Fuel Cells.

It is crucial to clarify the permeation behavior of O2 through the ionomer film for enhancing local O2 transport in cathodes of fuel cells. However, all existing studies mainly deal with pure O2 rather than air. Herein, the permeation behavior of the O2/N2 mixture through the ionomer film has been well explored in view of molecular bond length variations by molecular dynamics simulations. The bond lengths for O2 and N2 are shortened under a low hydration level when permeating through a dense layer with small free voids while no obvious change occurs at higher hydration. In the bulk ionomer region, O2 molecules residing in water domains are energetically unstable because the bond lengths deviate far from the equilibrium length; thus, O2 diffuses through the interfacial or hydrophobic regions. N2 molecules show similar properties with O2. This study provides a novel perspective on the permeation behavior of O2 and N2 through the ionomer film, which definitely benefits enhancing local O2 transport.

Platinum-Based Nanocomposite Pt@BSA as an Efficient Electrochemical Biosensing Interface for Rapid and Ultrasensitive Determination of Folate Receptor-Positive Tumor Cells.

Developing a cytosensing strategy based on electrochemical approaches has attracted wide interest due to the low cost, rapid response, and simple instrumentation. In this work, an electrochemical cytosensor employing the Pt@BSA nanocomposite as the biosensing substrate along with the covalent cross-linking of targeting molecules folic acid (FA) was constructed for highly sensitive determination of folate receptor (FR)-positive tumor cells. The prepared Pt@BSA nanocomposite revealed excellent biocompatibility for cell adhesion and proliferation, which was confirmed by cell viability evaluation using thiazolyl blue tetrazolium bromide (MTT) colorimetric methods. Due to the satisfactory electrical conductivity originating from Pt@BSA and the high binding affinity of FA to FR on the cell surface, an ultrasensitive and specific cytosensing device was designed for rapid and quantitative determination of HeLa cells (a model system) by differential pulse voltammetry (DPV) tests. This proposed cytosensor resulted in a wide HeLa cell determination range of 2.8 × 101-2.8 × 106 cells mL-1 with a low DPV detection limit of 9 cells mL-1. The developed cytosensing approach exhibited highly specific recognition of FR-positive tumor cells, excellent inter-assay reproducibility with a relative standard deviation (RSD) of 4.7%, acceptable intra-assay precision, and favorable storage stability, expanding the application of electrochemical measurement technology in the biomedical field of early detection and diagnosis of cancers.

Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance.

Green synthesis of ammonia by electrochemical nitrogen reduction reaction (NRR) shows great potential as an alternative to the Haber-Bosch process but is hampered by sluggish production rate and low Faradaic efficiency. Recently, lithium-mediated electrochemical NRR has received renewed attention due to its reproducibility. However, further improvement of the system is restricted by limited recognition of its mechanism. Herein, we demonstrate that lithium-mediated NRR began with electrochemical deposition of lithium, followed by two chemical processes of dinitrogen splitting and protonation to ammonia. Furthermore, we quantified the extent to which the freshly deposited active lithium lost its activity toward NRR due to a parasitic reaction between lithium and electrolyte. A high ammonia yield of 0.410 ± 0.038 µg s-1 cm-2 geo and Faradaic efficiency of 39.5 ± 1.7% were achieved at 20 mA cm-2 geo and 10 mA cm-2 geo, respectively, which can be attributed to fresher lithium obtained at high current density.

Optimizing the structural design of a nanocomposite catalyst layer for PEM fuel cells for improving mass-specific power density.

For the purpose of redesigning a PEM fuel cell with ultralow Pt loading, this review comprehensively summarizes and comments on recent important findings on ultrathin catalyst layer structures. We introduce recent advances in electrocatalyst research and development (R&D), highlighting the urgency of ultralow Pt loading in the total design of PEM fuel cells. Following that, the reason for a thinner and more ordered electrode structure is presented for the next generation of PEM fuel cells. We then review recent progress in methods for preparing Pt nanoparticles on high-aspect-ratio supports, extended surface area of nanowires (confined agglomerates and nanowires) and ordered arrays. Regarding the ordered arrays, we expatiate on proton conductor arrays and electron conductor arrays, including carbon nanotube-assisted arrays, TiO2 nanotube-assisted arrays, Co-OH-CO3 nanowire-assisted arrays, and pigment red 149-assisted arrays. Challenges related to proton transport and transfer, electron conduction and mass transport are then discussed to supply further research direction.

Voltage Cycling-Induced Pt Degradation in Proton Exchange Membrane Fuel Cells: Effect of Cycle Profiles.

To understand the processes of voltage cycling-induced catalyst degradation, influence of cycle profiles on Pt degradation is investigated using a mathematical method. Results show that the electrochemical surface area (ECSA) loss rate increases significantly with longer dwell time at the upper potential limit (UPL), which is mainly attributed to the enhanced Pt mass loss. The scan rate is also found to have little impact on the ECSA loss in the range of 1-37.5 mV/s as a lower scan rate will increase the Pt mass loss but mitigate Ostwald ripening. However, too long dwell time at the UPL or too slow scan rate would promote the formation of a more steady-state Pt oxide coverage, which is speculated to mitigate Pt dissolution. Decreasing cycle number has also been demonstrated to be the main contributor to the lower ECSA loss due to Ostwald ripening. Additionally, Ostwald ripening and Pt mass loss have comparable contributions to catalyst degradation at the UPL ≤ 0.9 V, while Pt mass loss contributes more at a higher UPL, which suggests that different load cycling strategies should be proposed for mitigating catalyst degradation at different UPLs.

A Comprehensive Investigation on Pyrolyzed Fe-N-C Composites as Highly Efficient Electrocatalyst toward the Oxygen Reduction Reaction of PEMFCs.

There remain great challenges in exploring cost-effective and highly efficient non-noble metal electrocatalysts to catalyze the oxygen reduction reaction (ORR) of proton exchange membrane fuel cells (PEMFCs). Also, a further validation on their performances under a fuel cell operating condition draws sustained attention. Herein, we report a comprehensive investigation on the ORR performances of a series of pyrolyzed Fe-N-C composites that use phenanthrolene as the nitrogen precursor, and the effects of carbon supports, transition metal precursors, and annealing temperatures are examined in detail. Electrochemical measurements combined with different physicochemical characterizations are employed to clarify the function of critical structures including the specific surface area, microstructure, nitrogen content, nitrogen type, and corresponding proportion on their ORR and fuel cell performances. It demonstrates a half-wave potential of 0.79 V and almost a four-electron pathway. When using the as-optimized Fe-N-C composite as the cathode catalyst of a PEMFC, the maximum power density reaches as high as 540 mW cm-2.

Icosahedral Pt-Ni Nanocrystalline Electrocatalyst: Growth Mechanism and Oxygen Reduction Activity.

Engineering the structure of Pt alloy offers an effective way to the design of high performance electrocatalysts. Herein, we synthesize a sandwich-structured, icosahedral Pt2.1 Ni catalyst through a hot injection method. Its growth involves three steps: 1) burst nucleation of Pt atoms to form a Pt-enriched core, 2) heterogeneous nucleation of Ni atoms onto the Pt core to form a Ni-enriched interlayer, and 3) kinetic controlled growth of a Pt-enriched shell. The Pt-enriched core protects the nanostructure from collapse and mitigates the strain change caused by lattice mismatch, and thus enhances the stability of the structure. The Ni-enriched interlayer induces the electronic modification of the outermost Pt shell, and in turn tunes the activity. The Pt-enriched shell provides more active sites through the exposure of (1 1 1) facets and retards the dissolution of Ni atoms. As a result, this sandwich-structure enables impressive electrocatalytic activity (0.91 mA cm-2 and 0.32 AmgPt-1 @ 0.9 V) and duability.

The Experimental Measurement of Local and Bulk Oxygen Transport Resistances in the Catalyst Layer of Proton Exchange Membrane Fuel Cells.

Remarkable progress has been made in reducing the cathodic Pt loading of PEMFCs; however, a huge performance loss appears at high current densities, indicating the existence of a large oxygen transport resistance associated with the ultralow Pt loading catalyst layer. To reduce the Pt loading without sacrificing cell performance, it is essential to illuminate the oxygen transport mechanism in the catalyst layer. Toward this goal, an experimental approach to measure the oxygen transport resistance in catalyst layers is proposed and realized for the first time in this study. The measuring approach involves a dual-layer catalyst layer design, which consists of a dummy catalyst layer and a practical catalyst layer, followed by changing the thickness of dummy layer to respectively quantify the local and bulk resistances via limiting current measurements combined with linear extrapolation. The experimental results clearly reveal that the local resistance dominates the total resistance in the catalyst layer.