Highly Selective N2 Electroreduction to NH3 Using a Boron-Vacancy-Rich Diatomic NbB Catalyst.

The ambient electrochemical N2 reduction reaction (NRR) is a future approach for the artificial NH3 synthesis to overcome the problems of high-energy consumption and environmental pollution by Haber-Bosch technology. However, the challenge of N2 activation on a catalyst surface and the competitive hydrogen evolution reaction make the current NRR unsatisfied. Herein, this work demonstrates that NbB2 nanoflakes (NFs) exhibit excellent selectivity and durability in NRR, which produces NH3 with a production rate of 30.5 µg h-1 mgcat -1 and a super-high Faraday efficiency (FE) of 40.2%. The high-selective NH3 production is attributed to the large amount of active B vacancies on the surface of NbB2 NFs. Density functional theory calculations suggest that the multiple atomic adsorption of N2 on both unsaturated Nb and B atoms results in a significantly stretched N2 molecule. The weakened NN triple bonds are easier to be broken for a biased NH3 production. The diatomic catalysis is a future approach for NRR as it shows a special N2 adsorption mode that can be well engineered.

Nitrate-to-Ammonia Conversion at an InSn-Enriched Liquid-Metal Electrode.

The renewable energy driven electrochemical conversion of nitrates to ammonia is emerging as a viable route for the creation of this hydrogen carrier. However, the creation of highly efficient electrocatalysts that show prolonged stability is an ongoing challenge. Here we show that room temperature liquid metal Galinstan can be used as an efficient and stable electrocatalyst for nitrate conversion to ammonia achieving rates of up to 2335 µg h-1 cm-2 with a Faradaic efficiency of 100 %. Density functional theory (DFT) calculations and experimental observation indicated the activity is due to InSn alloy enrichment within the liquid metal that occurs during the electrocatalytic reaction. This high selectivity for NH3 is also due to additional suppression of the competing hydrogen evolution reaction at the identified In3 Sn active site. This work adds to the increasing applicability of liquid metals based on Ga for clean energy technologies.

Griffith criterion for brittle fracture in graphene.

There are prevailing concerns with the critical dimensions when conventional theories break down. Here we find that the Griffith criterion remains valid for cracks down to 10 nm but overestimates the strength of shorter cracks. We observe the preferred crack extension along the zigzag edge in graphene, and explain this phenomenon by local strength-based failure rather than energy-based Griffith criterion. These results provide a mechanistic basis for reliable applications of graphene in miniaturized devices and nanocomposites.

Electrostatically induced Furfural-Derived carbon Dots-CdS hybrid for solar Light-Driven hydrogen production.

Carbon dots (CDs) exhibit distinctive optical, electronic, and physicochemical properties, rendering them effective cocatalysts to enhance the photocatalytic performance of light-absorbing materials. The interplay between CDs and substrates is pivotal in manipulating photogenerated charge separation, transfer, and redistribution, significantly influencing overall photocatalytic efficiency. This study introduces a novel electrostatic interaction strategy to interface positively charged CdS nanorods (CdS NRs) with negatively charged furfural-derived CDs. The resulting optimized composite (25-CDs@CdS NRs), showcases photocatalytic hydrogen production at a rate of 1076 µmol g-1h-1. Experimental analyses and theoretical simulations offer insights into the structure-activity relationship, underscoring the crucial role of enhanced electrostatic interaction between CDs and CdS NRs in facilitating efficient charge transfer, activating reaction sites, and improving reaction kinetics. This research establishes an adaptable strategy for integrating CDs with metal-based semiconductors, opening new avenues for developing photocatalytic hybrid assemblies.

Computational electrocatalysis beyond conventional hydrogen electrode model: CO2 reduction to C2 species on copper facilitated by dynamically formed solvent halide ions at the solid-liquid interface.

The reduction of CO2 into value-added chemicals and fuels has been actively studied as a promising strategy for mitigating carbon dioxide emissions. However, the dilemma for the experimentalist in choosing an appropriate reaction medium and neglecting the effect of solvent ions when using a simple thermochemical model, normally leads to the disagreement between experimental observations and theoretical calculations. In this work, by considering the effects of both the anion and cation, a more realistic CO2 reduction environment at the solid-liquid interface between copper and solvent ions has been systematically studied by using ab initio molecular dynamics and density functional theory. We revealed that the co-occurrence of alkali ions (K+) and halide ions (F-, Cl-, Br-, and I-) in the electric double layer (EDL) can enhance the adsorption of CO2 by more than 0.45 eV compared to that in pure water, and the calculated energy barrier for CO-CO coupling also decreases 0.32 eV in the presence of I ion on a negatively charged copper electrode. The hydrated ions can modulate the distribution of the charge near the solid-liquid interface, which significantly promotes CO2 reduction and meanwhile impedes the hydrogen evolution reaction. Therefore, our work unveils the significant role of halide ions at the electrode-electrolyte interface for promoting CO2 reduction on copper electrode.

The nature of strength enhancement and weakening by pentagon-heptagon defects in graphene.

The two-dimensional crystalline structures in graphene challenge the applicability of existing theories that have been used for characterizing its three-dimensional counterparts. It is crucial to establish reliable structure-property relationships in the important two-dimensional crystals to fully use their remarkable properties. With the success in synthesizing large-area polycrystalline graphene, understanding how grain boundaries (GBs) in graphene alter its physical properties is of both scientific and technological importance. A recent work showed that more GB defects could counter intuitively give rise to higher strength in tilt GBs (ref. 10). We show here that GB strength can either increase or decrease with the tilt, and the behaviour can be explained well by continuum mechanics. It is not just the density of defects that affects the mechanical properties, but the detailed arrangements of defects are also important. The strengths of tilt GBs increase as the square of the tilt angles if pentagon-heptagon defects are evenly spaced, and the trend breaks down in other cases. We find that mechanical failure always starts from the bond shared by hexagon-heptagon rings. Our present work provides fundamental guidance towards understanding how defects interact in two-dimensional crystals, which is important for using high-strength and stretchable graphene for biological and electronic applications.

Theoretical Evaluation of Highly Efficient Nitrate Reduction to Ammonia on InBi.

Electrocatalytic reduction of nitrate to ammonia has become a popular approach for wastewater treatment and ammonia production. However, the development of highly efficient electrocatalysts remains a great challenge. Herein, we systematically studied the potential of InBi for nitrate reduction to ammonia (NRA) based on density functional theory (DFT) calculations. Our results reveal that InBi exhibits high activity for NRA via an O-end pathway, where the free energy evolution of all intermediates is downhill in the most favorable elementary steps. The activation of nitrate originates from the strong orbital hybridization between oxygen and indium atoms, leading to an enhanced charge transfer as well as NO3- adsorption. In particular, the competing hydrogen evolution reaction (HER) is effectively suppressed due to the weak adsorption of proton. Our study not only proves the great electrocatalytic potential of InBi as a novel catalyst for NRA but also points out a new way to design NRA electrocatalysts for practical applications.

Charge transfer and vacancy engineering of Fe2O3 nanoparticle catalysts for highly selective N2 reduction towards NH3 synthesis.

The development of electrocatalysts for N2 reduction reaction (NRR) is significant for scalable and renewable NH3 synthesis, but calls for a technology innovation to overcome the specific problems of low efficiency and poor selectivity. Herein, we prepare a core-shell nanostructure by coating polypyrrole (PPy) onto sulfur-doped iron oxide nanoparticles (denoted as S-Fe2O3@PPy) as the highly selective and durable electrocatalysts for NRR under ambient conditions. Sulfur doping and PPy coating remarkably improve the charge transfer efficiency of S-Fe2O3@PPy, and the interactions between PPy and Fe2O3 nanoparticles produce abundant oxygen vacancies as active sites for NRR. This catalyst achieves an NH3 production rate of 22.1 µg h-1 mgcat-1 and a very-high Faradic efficiency of 24.6%, surpassing other Fe2O3 based NRR catalysts. Density functional theory calculations show that the S-coordinated iron site can successfully activate the N2 molecule and optimize the energy barrier during the reduction process, resulting in a small theoretical limiting potential.

Revealing the Potential of Ternary Medium-Entropy Alloys as Exceptional Electrocatalysts toward Nitrogen Reduction: An Example of Heusler Alloys.

With less energy consumption and environmental pollution, electrochemical ammonia synthesis is regarded as the most promising way to replace the industrial Haber-Bosch process, which greatly contributes to global energy consumption and CO2 emission. At present, the best metal electrocatalyst for N2 fixation is ruthenium although its performance still suffers from a low Faradaic efficiency and a high overpotential. Alloy engineering is a promising way to discover more metal-based electrocatalysts for dinitrogen reduction reaction (N2RR), and almost all reported alloy catalysts so far are binary alloys. In this work, we proposed a large group of ternary alloy electrocatalysts (Heusler alloys) for N2RR and demonstrated their superior catalytic performance. As an example, alloying Ru with Mn and Si led to a reduced Ru-Ru distance on the surface, which facilitates an uncommon horizontal adsorption mode of N2 and results in effective activation of N2 molecules. The theoretical overpotential of N2RR on Ru2MnSi(100-Ru) is only around 0.28 V, which ranks among the best reported results, and the usage of precious Ru is greatly reduced. Meanwhile, the adsorption of N2 on Ru2MnSi(100-Ru) was much stronger than that of protons, and it also took less energy to drive N2RR than the hydrogen evolution reaction (HER), making HER less competitive on this catalyst. Considering the successful synthesis of numerous Heusler alloys including the six members mentioned here, our work provided a wider range of practical and excellent N2RR electrocatalysts in terms of both catalytic performance and economical cost.