NH3 Electrosynthesis from N2 Molecules: Progresses, Challenges, and Future Perspectives.

Green ammonia (NH3), made by using renewable electricity to split nearly limitless nitrogen (N2) molecules, is a vital platform molecule and an ideal fuel to drive the sustainable development of human society without carbon dioxide emission. The NH3 electrosynthesis field currently faces the dilemma of low yield rate and efficiency; however, decoupling the overlapping issues of this area and providing guidelines for its development directions are not trivial because it involves complex reaction process and multidisciplinary entries (for example, electrochemistry, catalysis, interfaces, processes, etc.). In this Perspective, we introduce a classification scheme for NH3 electrosynthesis based on the reaction process, namely, direct (N2 reduction reaction) and indirect electrosynthesis (Li-mediated/plasma-enabled NH3 electrosynthesis). This categorization allows us to finely decouple the complicated reaction pathways and identify the specific rate-determining steps/bottleneck issues for each synthesis approach such as N2 activation, H2 evolution side reaction, solid-electrolyte interphase engineering, plasma process, etc. We then present a detailed overview of the latest progresses on solving these core issues in terms of the whole electrochemical system covering the electrocatalysts, electrodes, electrolytes, electrolyzers, etc. Finally, we discuss the research focuses and the promising strategies for the development of NH3 electrosynthesis in the future with a multiscale perspective of atomistic mechanisms, nanoscale electrocatalysts, microscale electrodes/interfaces, and macroscale electrolyzers/processes. It is expected that this Perspective will provide the readers with an in-depth understanding of the bottleneck issues and insightful guidance on designing the efficient NH3 electrosynthesis systems.

FeOOH with Low Spin State Iron as Electron Acceptors for High Yield Rate Electrosynthesis of Urea from Nitrate and Carbon Dioxide.

Co electroreduction of carbon dioxide and nitrate to synthesize urea provides an alternative strategy to high energy-consumption traditional methods. However, the complexity of the reaction mechanism and the high energy barrier of nitrate reduction result in a diminished production of urea. Herein, a convenient electrodeposition technique to prepare the FeOOH with low spin state iron that increases the yield rate of urea efficiently is employed. According to soft X-ray Absorption Spectroscopy and theoretical calculations, the unique configuration of low spin state iron as electron acceptors can effectively induce electron pair transfer from the occupied σ orbitals of intermediate * NO to empty d orbitals of iron. This σ→d donation mechanism leads to a reduction in the energy barrier associated with the rate-determining step (* NOOH→* NO + * OH), hence augmenting the urea generation. The low spin state iron presents a high urea yield rate of 512 µg h-1  cm-2 , representing approximately two times compared to the medium spin state iron. The key intermediates (* NH2 and * CO) in the formation of C─N bond are detected with in situ Fourier transform infrared spectroscopy. The coupling of * NH2 and * CO contributes to the formation of * CONH2 , which subsequently endures multi-step proton-coupled electron transfer to generate urea.

A Bio-Inspired Methylation Approach to Salt-Concentrated Hydrogel Electrolytes for Long-Life Rechargeable Batteries.

Hydrogel electrolytes hold great promise in developing flexible and safe batteries, but the presence of free solvent water makes battery chemistries constrained by H2 evolution and electrode dissolution. Although maximizing salt concentration is recognized as an effective strategy to reduce water activity, the protic polymer matrices in classical hydrogels are occupied with hydrogen-bonding and barely involved in the salt dissolution, which sets limitations on realizing stable salt-concentrated environments before polymer-salt phase separation occurs. Inspired by the role of protein methylation in regulating intracellular phase separation, here we transform the "inert" protic polymer skeletons into aprotic ones through methylation modification to weaken the hydrogen-bonding, which releases free hydrogen bond acceptors as Lewis base sites to participate in cation solvation and thus assist salt dissolution. An unconventionally salt-concentrated hydrogel electrolyte reaching a salt fraction up to 44 mol % while retaining a high Na+ /H2 O molar ratio of 1.0 is achieved without phase separation. Almost all water molecules are confined in the solvation shell of Na+ with depressed activity and mobility, which addresses water-induced parasitic reactions that limit the practical rechargeability of aqueous sodium-ion batteries. The assembled Na3 V2 (PO4 )3 //NaTi2 (PO4 )3 cell maintains 82.8 % capacity after 580 cycles, which is the longest cycle life reported to date.

Microscopic-Level Insights into the Mechanism of Enhanced NH3 Synthesis in Plasma-Enabled Cascade N2 Oxidation-Electroreduction System.

Integrated/cascade plasma-enabled N2 oxidation and electrocatalytic NOx- (where x = 2, 3) reduction reaction (pNOR-eNOx-RR) holds great promise for the renewable synthesis of ammonia (NH3). However, the corresponding activated effects and process of plasma toward N2 and O2 molecules and the mechanism of eNOx-RR to NH3 are unclear and need to be further uncovered, which largely limits the large-scale deployment of this process integration technology. Herein, we systematically investigate the plasma-enabled activation and recombination processes of N2 and O2 molecules, and more meaningfully, the mechanism of eNOx-RR at a microscopic level is also decoupled using copper (Cu) nanoparticles as a representative electrocatalyst. The concentration of produced NOx in the pNOR system is confirmed as a function of the length for spark discharge as well as the volumetric ratio for N2 and O2 feeding gas. The successive protonation process of NOx- and the key N-containing intermediates (e.g., -NH2) of eNOx-RR are detected with in situ infrared spectroscopy. Besides, in situ Raman spectroscopy further reveals the dynamic reconstruction process of Cu nanoparticles during the eNOx-RR process. The Cu nanoparticle-driven pNOR-eNOx-RR system can finally achieve a high NH3 yield rate of ∼40 nmol s-1 cm-2 and Faradaic efficiency of nearly 90%, overperforming the benchmarks reported in the literature. It is anticipated that this work will stimulate the practical development of the pNOR-eNOx-RR system for the green electrosynthesis of NH3 directly from air and water under ambient conditions.

Recognition of Water-Induced Effects toward Enhanced Interaction between Catalyst and Reactant in Alcohol Oxidation.

Pickering emulsion stabilized by solid nanoparticles provides a diverse solvent microenvironment and enables to promote the phase transfer of reaction substrates/products in catalytic reactions, but the intrinsic role of solvent is still not clear. Herein, using benzyl alcohol (BA) as a model reactant, we demonstrate the nature of the water-promoted activity for alcohol oxidation over the Pd/MgAl-LDO catalyst. Depending on the water in the solvent, we observe different reactivities regarding the proportion of the water in the system. Kinetic isotope effects confirm the participation and positive effects of water for oxidation of BA. The water promotion effects are recognized and identified by the water vapor pulse adsorption coupled with temperature program desorption. Moreover, the adsorption behavior of BA or benzaldehyde at the interface of water and Pd/MgAl-LDO is also investigated by quasi-in-situ Raman spectroscopy. In addition, the mechanism of water-promoted alcohol oxidation is rationally proposed based on the Langmuir-Hinshelwood mechanism. The general applicability of the water promotion effects is further demonstrated over different supports and substrates, which well achieves excellent catalytic activity and selectivity in Pickering emulsion compared to that in the pure toluene system.

A Dual-Cation Exchange Membrane Electrolyzer for Continuous H2 Production from Seawater.

Direct seawater splitting (DSS) offers an aspirational route toward green hydrogen (H2) production but remains challenging when operating in a practically continuous manner, mainly due to the difficulty in establishing the water supply-consumption balance under the interference from impurity ions. A DSS system is reported for continuous ampere-level H2 production by coupling a dual-cation exchange membrane (CEM) three-compartment architecture with a circulatory electrolyte design. Monovalent-selective CEMs decouple the transmembrane water migration from interferences of Mg2+, Ca2+, and Cl- ions while maintaining ionic neutrality during electrolysis; the self-loop concentrated alkaline electrolyte ensures the constant gradient of water chemical potential, allowing a specific water supply-consumption balance relationship in a seawater-electrolyte-H2 sequence to be built among an expanded current range. Even paired with commercialized Ni foams, this electrolyzer (model size: 2 × 2 cm2) continuously produces H2 from flowing seawater with a rate of 7.5 mL min-1 at an industrially relevant current of 1.0 A over 100 h. More importantly, the energy consumption can be further reduced by coupling more efficient NiMo/NiFe foams (≈6.2 kWh Nm-3 H2 at 1.0 A), demonstrating the potential to further optimize the continuous DSS electrolyzer for practical applications.

A Bioinspired Membrane with Ultrahigh Li+/Na+ and Li+/K+ Separations Enables Direct Lithium Extraction from Brine.

Membranes with precise Li+/Na+ and Li+/K+ separations are imperative for lithium extraction from brine to address the lithium supply shortage. However, achieving this goal remains a daunting challenge due to the similar valence, chemical properties, and subtle atomic-scale distinctions among these monovalent cations. Herein, inspired by the strict size-sieving effect of biological ion channels, a membrane is presented based on nonporous crystalline materials featuring structurally rigid, dimensionally confined, and long-range ordered ion channels that exclusively permeate naked Li+ but block Na+ and K+. This naked-Li+-sieving behavior not only enables unprecedented Li+/Na+ and Li+/K+ selectivities up to 2707.4 and 5109.8, respectively, even surpassing the state-of-the-art membranes by at least two orders of magnitude, but also demonstrates impressive Li+/Mg2+ and Li+/Ca2+ separation capabilities. Moreover, this bioinspired membrane has to be utilized for creating a one-step lithium extraction strategy from natural brines rich in Na+, K+, and Mg2+ without utilizing chemicals or creating solid waste, and it simultaneously produces hydrogen. This research has proposed a new type of ion-sieving membrane and also provides an envisioning of the design paradigm and development of advanced membranes, ion separation, and lithium extraction.

The emerging roles of retromer and sorting nexins in the life cycle of viruses.

Retromer and sorting nexins (SNXs) transport cargoes from endosomes to the trans-Golgi network or plasma membrane. Recent studies have unveiled the emerging roles for retromer and SNXs in the life cycle of viruses, including members of Coronaviridae, Flaviviridae and Retroviridae. Key components of retromer/SNXs, such as Vps35, Vps26, SNX5 and SNX27, can affect multiple steps of the viral life cycle, including facilitating the entry of viruses into cells, participating in viral replication, and promoting the assembly of virions. Here we present a comprehensive updated review on the interplay between retromer/SNXs and virus, which will shed mechanistic insights into controlling virus infection.