Encapsulating metal organic framework into hollow mesoporous carbon sphere as efficient oxygen bifunctional electrocatalyst

Applying metal organic frameworks (MOFs) in electrochemical systems is a currently emerging field owing to the rich metal nodes and highly specific surface area of MOFs. However, the problems for MOFs that need to be solved urgently are poor electrical conductivity and low ion transport. Here we present a facile in situ growth method for the rational synthesis of MOFs@hollow mesoporous carbon spheres (HMCS) yolk–shell-structured hybrid material for the first time. The size of the encapsulated Zeolitic Imidazolate Framework-67 (ZIF-67) is well controlled to 100 nm due to the spatial confinement effect of HMCS, and the electrical conductivity of ZIF-67 is also increased significantly. The ZIF@HMCS-25% hybrid material obtained exhibits a highly efficient oxygen reduction reaction activity with 0.823 V (vs. reversible hydrogen electrode) half-wave potential and an even higher kinetic current density (J_K = 13.8 mA cm⁻²) than commercial Pt/C. ZIF@HMCS-25% also displays excellent oxygen evolution reaction performance and the overpotential of ZIF@HMCS-25% at 10 mA cm⁻² is 407 mV. In addition, ZIF@HMCS-25% is further employed as an air electrode for a rechargeable Zn–air battery, exhibiting a high power density (120.2 mW cm⁻² at 171.4 mA cm⁻²) and long-term charge/discharge stability (80 h at 5 mA cm⁻²). This MOFs@HMCS yolk–shell design provides a versatile method for the application of MOFs as electrocatalysts directly.     

阳极电催化剂在直接甲醇燃料电池的应用

直接甲醇燃料电池以燃料甲醇来源丰富，价格低廉，储存、携带方便而成为近年的研究热点。本文评述了阳极催化剂在直接甲醇燃料电池的研究概况，详细介绍了多种催化剂对甲醇氧化的作用。     

Tracking structural evolution: operando regenerative CeOx/Bi interface structure for high-performance CO2 electroreduction

Unveiling the structural evolution and working mechanism of catalysts under realistic operating conditions is crucial for the design of efficient electrocatalysts for CO₂ electroreduction, yet remains highly challenging. Here, by virtue of operando structural measurements at multiscale levels, it is identified under CO₂ electroreduction conditions that an as-prepared CeO₂/BiOCl precatalyst gradually evolves into CeO_x/Bi interface structure with enriched Ce³⁺ species, which serves as the real catalytically active phase. The derived CeO_x/Bi interface structure compared to pure Bi counterpart delivers substantially enhanced performance with a formate Faradaic efficiency approaching 90% for 24 hours in a wide potential window. The formate Faradaic efficiency can be further increased by using isotope D₂O instead of H₂O. Density functional theory calculations suggest that the regenerative CeO_x/Bi interfacial sites can not only promote water activation to increase local ^*H species for CO₂ protonation appropriately, but also stabilize the key intermediate ^*OCHO in formate pathway.     

A highly efficient atomically thin curved PdIr bimetallene electrocatalyst

The multi-metallene with an ultrahigh surface area has great potential in precise tuning of surface heterogeneous d-electronic correlation by surface strain effect for the distinctive surface electronic structure, which is a brand new class of promising 2D electrocatalyst for sustainable energy device application. However, achieving such an atomically thin multi-metallene still presents a great challenge. Herein, we present a new synthetic method for an atomic-level palladium-iridium (PdIr) bimetallene with an average thickness of only ∼1.0 nm for achieving superior catalysis in the hydrogen evolution reaction (HER) and the formic acid oxidation reaction (FAOR). The curved PdIr bimetallene presents a top-ranked high electrochemical active area of 127.5 ± 10.8 m² g_Pd+Ir⁻¹ in the reported noble alloy materials, and exhibits a very low overpotential, ultrahigh activity and improved stability for HER and FAOR. DFT calculation reveals that the PdIr bimetallene herein has a unique lattice tangential strain, which can induce surface distortion while concurrently creating a variety of concave-convex featured micro-active regions formed by variously coordinated Pd sites agglomeration. Such a strong strain effect correlates the abnormal on-site active 4d¹⁰-t_2g-orbital Coulomb correlation potential and directly elevates orbital-electronegativity exposure within these active regions, resulting in a preeminent barrier-free energetic path for significant enhancement of FAOR and HER catalytic performance.     

玻碳负载Pt催化剂的制备及对甲醇的电催化氧化

用两步循环伏安法制备了Pt/GC电极，并采用电化学方法、X射线衍射法XRD和电镜对该电极进行了表征，研究了该电极对甲醇的电催化氧化性能，实验结果表明，Pt/GC电极显示出较高的电催化活性和稳定性；计算出传递系数．     

乙醇在Pt/SiO2-CNTs纳米催化剂上的电催化氧化

通过溶胶凝胶方法制备SiO2修饰的碳纳米管（SiO2-CNTs）为载体材料,利用微波辅助加热化学还原方法制备Pt/SiO2-CNTs电催化剂。然后分别利用扫描电子显微镜和能量散射谱仪对Pt/SiO2-CNTs电催化剂的表面形貌和元素组成进行了表征。在酸性介质中,采用循环伏安法研究了Pt/SiO2-C电催化剂对乙醇氧化的电催化活性。与商用催化剂PtRu/C电催化剂相比,在相同催化剂载量和实验条件下,Pt/SiO2-CNTs电催化剂具有更好的催化活性和抗CO中毒能力。     

Selective electrochemical production of hydrogen peroxide at zigzag edges of exfoliated molybdenum telluride nanoflakes

The two-electron reduction of molecular oxygen represents an effective strategy to enable the green, mild and on-demand synthesis of hydrogen peroxide. Its practical viability, however, hinges on the development of advanced electrocatalysts, preferably composed of non-precious elements, to selectively expedite this reaction, particularly in acidic medium. Our study here introduces 2H-MoTe₂ for the first time as the efficient non-precious-metal-based electrocatalyst for the electrochemical production of hydrogen peroxide in acids. We show that exfoliated 2H-MoTe₂ nanoflakes have high activity (onset overpotential ∼140 mV and large mass activity of 27 A g⁻¹ at 0.4 V versus reversible hydrogen electrode), great selectivity (H₂O₂ percentage up to 93%) and decent stability in 0.5 M H₂SO₄. Theoretical simulations evidence that the high activity and selectivity of 2H-MoTe₂ arise from the proper binding energies of HOO^* and O^* at its zigzag edges that jointly favor the two-electron reduction instead of the four-electron reduction of molecular oxygen.