Interfacial "Double-Terminal Binding Sites" Catalysts Synergistically Boosting the Electrocatalytic Li2S Redox for Durable Lithium-Sulfur Batteries.

Catalytic conversion of polysulfides emerges as a promising approach to improve the kinetics and mitigate polysulfide shuttling in lithium-sulfur (Li-S) batteries, especially under conditions of high sulfur loading and lean electrolyte. Herein, we present a separator architecture that incorporates double-terminal binding (DTB) sites within a nitrogen-doped carbon framework, consisting of polar Co0.85Se and Co clusters (Co/Co0.85Se@NC), to enhance the durability of Li-S batteries. The uniformly dispersed clusters of polar Co0.85Se and Co offer abundant active sites for lithium polysulfides (LiPSs), enabling efficient LiPS conversion while also serving as anchors through a combination of chemical interactions. Density functional theory calculations, along with in situ Raman and X-ray diffraction characterizations, reveal that the DTB effect strengthens the binding energy to polysulfides and lowers the energy barriers of polysulfide redox reactions. Li-S batteries utilizing the Co/Co0.85Se@NC-modified separator demonstrate exceptional cycling stability (0.042% per cycle over 1000 cycles at 2 C) and rate capability (849 mAh g-1 at 3 C), as well as deliver an impressive areal capacity of 10.0 mAh cm-2 even in challenging conditions with a high sulfur loading (10.7 mg cm-2) and lean electrolyte environments (5.8 µL mg-1). The DTB site strategy offers valuable insights into the development of high-performance Li-S batteries.

Fundamentally Manipulating the Electronic Structure of Polar Bifunctional Catalysts for Lithium-Sulfur Batteries: Heterojunction Design versus Doping Engineering.

Heterogeneous structures and doping strategies have been intensively used to manipulate the catalytic conversion of polysulfides to enhance reaction kinetics and suppress the shuttle effect in lithium-sulfur (Li-S) batteries. However, understanding how to select suitable strategies for engineering the electronic structure of polar catalysts is lacking. Here, a comparative investigation between heterogeneous structures and doping strategies is conducted to assess their impact on the modulation of the electronic structures and their effectiveness in catalyzing the conversion of polysulfides. These findings reveal that Co0.125 Zn0.875 Se, with metal-cation dopants, exhibits superior performance compared to CoSe2 /ZnSe heterogeneous structures. The incorporation of low Co2+ dopants induces the subtle lattice strain in Co0.125 Zn0.875 Se, resulting in the increased exposure of active sites. As a result, Co0.125 Zn0.875 Se demonstrates enhanced electron accumulation on surface Se sites, improved charge carrier mobility, and optimized both p-band and d-band centers. The Li-S cells employing Co0.125 Zn0.875 Se catalyst demonstrate significantly improved capacity (1261.3 mAh g-1 at 0.5 C) and cycle stability (0.048% capacity delay rate within 1000 cycles at 2 C). This study provides valuable guidance for the modulation of the electronic structure of typical polar catalysts, serving as a design directive to tailor the catalytic activity of advanced Li-S catalysts.

Facile and Stable CuInO2 Nanoparticles for Efficient Electrochemical CO2 Reduction.

Searching for electrocatalysts for the electrochemical CO2 reduction reaction (e-CO2RR) with high selectivity and stability remains a significant challenge. In this study, we design a Cu-CuInO2 composite with stable states of Cu0/Cu+ by electrochemically depositing indium onto CuCl-decorated Cu foil. The catalyst displays superior selectivity toward the CO product, with a maximal Faraday efficiency of 89% at -0.9 V vs the reversible hydrogen electrode, and maintains impressive stability up to 27 h with a retention rate of >76% in Faraday efficiency. Our systematical characterizations reveal that the catalyst's high performance is attributed to CuInO2 nanoparticles. First-principles calculations further confirm that CuInO2(012) is more conducive to CO generation than Cu(111) under applied potential and presents a higher energy barrier than Cu(111) for the hydrogen evolution reaction. These theoretical predictions are consistent with our experimental observations, suggesting that CuInO2 nanoparticles offer a facile catalyst with a high selectivity and stability for e-CO2RR.

Multi-metal electrocatalyst with crystalline/amorphous structure for enhanced alkaline water/seawater hydrogen evolution.

The development of well-defined nanomaterials as non-noble metal electrocatalysts has broad application prospect for hydrogen generation technology. Recently, multi-metal electrocatalysts for hydrogen evolution reaction (HER) have attracted extensive attention due to their high catalytic performance arising from the synergistic effect of multi-metal interaction. However, most multi-metal catalysts suffer from the limited synergistic effect because of poor interfacial compatibility between different components. Here, a novel multi-metal catalyst (Ni/MoO2@CoFeOx) nanosheet with a crystalline/amorphous structure is demonstrated, which shows high HER activity. Ni/MoO2@CoFeOx exhibits an ultra-low overpotential of 18, 39, and 93 mV at 10 mA cm-2 in alkaline water, alkaline seawater and natural seawater, respectively, which outperformances most of the state-of-the-art non-noble metal compounds. In addition, the catalyst shows exceptional stability under 500 mA cm-2 in alkaline solution. In-situ Raman and other advanced structural characterization confirms the excellent catalytic activity is mainly contributed by: (1) the strong synergistic effect of multi-metal components provides multiple active sites in the catalytic process; (2) the crystalline/amorphous interface in Ni/MoO2@CoFeOx boosts the catalytically active sites and structure stability; (3) the crystalline phase enhances the intrinsic conductivity greatly; and (4) the amorphous phase provides abundant unsaturated sites for improved intrinsic catalytic activity. This work provides a feasible way to design electrocatalyst with high activity and stability for practical applications.

Comprehensive Mechanism for CO Electroreduction on Dual-Atom-Catalyst-Anchored N-Doped Graphene.

Carbon neutrality has drawn increasing attention for realizing the carbon cyclization and reducing the greenhouse effect. Although the C1 products, such as CO, can be achieved with a high Faraday efficiency, the targeted production of C2 fuels as well as the mechanism have not been systematically investigated. In this work, we carry out a first-principles study to screen dual-atom catalysts (DACs) for producing C2 fuels through the electrocatalytic carbon monoxide reduction reaction (e-CORR). We find that methanol, ethanol and ethylene can be produced on both DAC-Co and DAC-Cu, while acetate can be achieved on DAC-Cu only. Importantly, methanol and ethylene are preferred on DAC-Co, while acetate and ethylene on DAC-Cu. Furthermore, we show that the explicit solvent can enhance the adsorption and influence the protonation steps, which subsequently affects the protonation and dimerization behavior as well as the performance and selectivity of e-CORR on DACs. We further demonstrate that the C-C coupling is easy to be formed and stabilized if the Integrated Crystal Orbital Hamilton Population (ICOHP) is low because of the low energy barrier. Our findings provide not only guidance on the design of novel catalysts for e-CORR, but an insightful understanding on the reduction mechanism.

Advances in Spin Catalysts for Oxygen Evolution and Reduction Reactions.

Searching for high effective catalysts has been an endless effort to improve the efficiency of green energy harvesting and degradation of pollutants. In the past decades, tremendous strategies are explored to achieve high effective catalysts, and various theoretical understandings are proposed for the improved activity. As the catalytic reaction occurs at the surface or edge, the unsaturated ions may lead to the fluctuation of spin. Meanwhile, transition metals in catalysts have diverse spin states and may yield the spin effects. Therefore, the role of spin or magnetic moment should be carefully examined. In this review, the recent development of spin catalysts is discussed to give an insightful view on the origins for the improved catalytic activity. First, a brief introduction on the applications and advances in spin-related catalytic phenomena, is given, and then the fundamental principles of spin catalysts and magnetic fields-radical reactions are introduced in the second part. The spin-related catalytic performance reported in oxygen evolution/reduction reaction (OER/ORR) is systematically discussed in the third part, and general rules are summarized accordingly. Finally, the challenges and perspectives are given. This review may provide an insightful understanding of the microscopic mechanisms of catalytic phenomena and guide the design of spin-related catalysts.

M4 B6 X6 as a New Family of High-Efficient Electrocatalysts: The Role of Surface Reconstruction in Water Oxidization.

Searching for highly-efficient electrocatalysts for water splitting has been greatly endowed due to the huge demand for green energy sources. Two-dimensional (2D) materials are widely explored for the purpose because of their unique physical and chemical properties, abundant active sites, and easy fabrication. Here, we present a new family of 2D M4 B6 X6 (2D Boridenes) and investigate their physical and chemical properties for their potential applications into electrocatalysis based on first-principles calculations. We demonstrate that 2D M4 B6 X6 (M=Cr, Mo, and W; X=O and F) are dynamically, thermodynamically, and mechanically stable, and show intriguing electronic and catalytic properties. Importantly, we find that M4 B6 O6 are intrinsically active for oxygen evolution reaction (OER). Our results demonstrate that: (1) the adsorbate-escape mechanism dominates the OER process with a low overpotential of 0.652 V on Cr4 B6 O6 ; (2) the partial surface-oxidization can improve the catalytic performance of M4 B6 F6 dramatically; and (3) the surface reconstruction greatly affects the OER performance of M4 B6 X6 . Our findings illustrate that the surface reconstruction is critical to the OER activity, which may provide a new strategy on the design of 2D materials for electrocatalysis and offer theoretical insight into the catalytic mechanism.

Development of Perovskite Oxide-Based Electrocatalysts for Oxygen Evolution Reaction.

Perovskite oxides are studied as electrocatalysts for oxygen evolution reactions (OER) because of their low cost, tunable structure, high stability, and good catalytic activity. However, there are two main challenges for most perovskite oxides to be efficient in OER, namely less active sites and low electrical conductivity, leading to limited catalytic performance. To overcome these intrinsic obstacles, various strategies are developed to enhance their catalytic activities in OER. In this review, the recent developments of these strategies is comprehensively summarized and systematically discussed, including composition engineering, crystal facet control, morphology modulation, defect engineering, and hybridization. Finally, perspectives on the design of perovskite oxide-based electrocatalysts for practical applications in OER are given.

WXy /g-C3 N4 (WXy =W2 C, WS2 , or W2 N) Composites for Highly Efficient Photocatalytic Water Splitting.

The development of earth-abundant, economical, and efficient photocatalysts to boost water splitting is a key challenge for the practical large-scale application of hydrogen energy. In this study, g-C3 N4 loaded with different tungsten compounds (W2 C, WS2 , and W2 N) is found to exhibit enhanced photocatalytic activities. W2 C/g-C3 N4 displays the highest activity for the photocatalytic reaction with a H2 evolution rate of up to 98 µmol h-1 , as well as remarkable recycling stability. The excellent photocatalytic activity of W2 C/g-C4 N3 is attributed to the suitable band alignment in W2 C/g-C4 N3 and high HER activity of the W2 C cocatalyst, which promotes the separation and transfer of carriers and hydrogen evolution at the surface. These findings demonstrate that the tungsten carbide cocatalyst is more active for the photocatalytic reaction than the sulfide or nitride, paving a way for the design of novel and efficient carbides as cocatalysts for photocatalysis.

Efficient nitrogen fixation to ammonia on MXenes.

Active catalysts for nitrogen fixation (N2-fixation) have been widely pursued through constant efforts for industrial applications. Here, we report a family of catalysts, MXenes (M2X: M = Mo, Ta, Ti, and W; X = C and N), for application in N2-fixation based on density functional theory calculations. We find that the catalytic performance of MXenes strongly depends on the reaction energy in each reaction step. More exothermic steps lead to higher catalytic performance in the course of N2-fixation. We show that the reaction energy in N2-fixation is strongly affected by the charge transfer: (1) if N atoms gain more electrons in a step, the reaction is exothermic with a larger reaction energy; (2) if N atoms lose electrons in a step, the reaction is endothermic in general. We further show that Mo2C and W2C are highly active for N2-fixation due to their exothermic reactions and strong charge transfer, which may be applicable in the chemical-engineering industry.

Post-boosting of classification boundary for imbalanced data using geometric mean.

In this paper, a novel imbalance learning method for binary classes is proposed, named as Post-Boosting of classification boundary for Imbalanced data (PBI), which can significantly improve the performance of any trained neural networks (NN) classification boundary. The procedure of PBI simply consists of two steps: an (imbalanced) NN learning method is first applied to produce a classification boundary, which is then adjusted by PBI under the geometric mean (G-mean). For data imbalance, the geometric mean of the accuracies of both minority and majority classes is considered, that is statistically more suitable than the common metric accuracy. PBI also has the following advantages over traditional imbalance methods: (i) PBI can significantly improve the classification accuracy on minority class while improving or keeping that on majority class as well; (ii) PBI is suitable for large data even with high imbalance ratio (up to 0.001). For evaluation of (i), a new metric called Majority loss/Minority advance ratio (MMR) is proposed that evaluates the loss ratio of majority class to minority class. Experiments have been conducted for PBI and several imbalance learning methods over benchmark datasets of different sizes, different imbalance ratios, and different dimensionalities. By analyzing the experimental results, PBI is shown to outperform other imbalance learning methods on almost all datasets.