Engineering Electronic Structure of Nitrogen-Carbon Sites by sp3 -Hybridized Carbon and Incorporating Chlorine to Boost Oxygen Reduction Activity.

Development of efficient and easy-to-prepare low-cost oxygen reaction electrocatalysts is essential for widespread application of rechargeable Zn-air batteries (ZABs). Herein, we mixed NaCl and ZIF-8 by simple physical milling and pyrolysis to obtain a metal-free porous electrocatalyst doped with Cl (mf-pClNC). The mf-pClNC electrocatalyst exhibits a good oxygen reduction reaction (ORR) activity (E1/2 =0.91 V vs. RHE) and high stability in alkaline electrolyte, exceeding most of the reported transition metal carbon-based electrocatalysts and being comparable to commercial Pt/C electrocatalysts. Likewise, the mf-pClNC electrocatalyst also shows state-of-the-art ORR activity and stability in acidic electrolyte. From experimental and theoretical calculations, the better ORR activity is most likely originated from the fact that the introduced Cl promotes the increase of sp3 -hybridized carbon, while the sp3 -hybridized carbon and Cl together modify the electronic structure of the N-adjacent carbons, as the active sites, while NaCl molten-salt etching provides abundant paths for the transport of electrons/protons. Furthermore, the liquid rechargeable ZAB using the mf-pClNC electrocatalyst as the cathode shows a fulfilling performance with a peak power density of 276.88 mW cm-2 . Flexible quasi-solid-state rechargeable ZAB constructed with the mf-pClNC electrocatalyst as the cathode exhibits an exciting performance both at low, high and room temperatures.

Dilute RuCo Alloy Synergizing Single Ru and Co Atoms as Efficient and CO-Resistant Anode Catalyst for Anion Exchange Membrane Fuel Cells.

Ruthenium (Ru) is considered a promising candidate catalyst for alkaline hydroxide oxidation reaction (HOR) due to its hydrogen binding energy (HBE) like that of platinum (Pt) and its much higher oxygenophilicity than that of Pt. However, Ru still suffers from insufficient intrinsic activity and CO resistance, which hinders its widespread use in anion exchange membrane fuel cells (AEMFCs). Here, we report a hybrid catalyst (RuCo)NC+SAs/N-CNT consisting of dilute RuCo alloy nanoparticles and atomically single Ru and Co atoms on N-doped carbon nanotubes The catalyst exhibits a state-of-the-art activity with a high mass activity of 7.35 A mgRu -1. More importantly, when (RuCo)NC+SAs/N-CNT is used as an anode catalyst for AEMFCs, its peak power density reaches 1.98 W cm-2, which is one of the best AEMFCs properties of noble metal-based catalysts at present. Moreover, (RuCo)NC+SAs/N-CNT has superior long-time stability and CO resistance. The experimental and density functional theory (DFT) results demonstrate that the dilute alloying and monodecentralization of the exotic element Co greatly modulates the electronic structure of the host element Ru, thus optimizing the adsorption of H and OH and promoting the oxidation of CO on the catalyst surface, and then stimulates alkaline HOR activity and CO tolerance of the catalyst.

Near-Atomic-Scale Superfine Alloy Clusters for Ultrastable Acidic Hydrogen Electrocatalysis.

As a commercial electrode material for proton-exchange membrane water electrolyzers and fuel cells, Pt-based catalysts still face thorny issues, such as insufficient mass activity, stability, and CO tolerance. Here, we construct a bifunctional catalyst consisting of Pt-Er alloy clusters and atomically dispersed Pt and Er single atoms, which exhibits excellent activity, durability, and CO tolerance of acidic hydrogen evolution and oxidation reactions (HER and HOR). The catalyst possesses a remarkably high mass activity and TOF for HER at 63.9 times and 7.2 times more than that of Pt/C, respectively. More impressively, it can operate stably in the acidic electrolyte at 1000 mA cm-2 for more than 1200 h, thereby confirming its potential for practical applications at the industrial current density. In addition, the catalyst also demonstrates a distinguished HOR performance and outstanding CO tolerance. The synergistic effects of active sites give the catalyst exceptional activity for the hydrogen reaction, while the introduction of Er atoms greatly enhances its stability and CO tolerance. This work provides a promising idea for designing low-Pt-loading acidic HER electrocatalysts that are durable at ampere-level current densities and for constructing HOR catalysts with high CO tolerance.

Recent Advances on Single-Atom Catalysts for Photocatalytic CO2 Reduction.

The present energy crisis and environmental challenges may be efficiently resolved by converting carbon dioxide (CO2 ) into various useful carbon products. The development of more effective catalysts has been the main focus of current research on photocatalytic CO2 reduction. Due to their high atomic efficiency and superior catalytic activity, single-atom catalysts (SACs) have attracted considerable interest in catalytic CO2 conversion. This review discusses the current research developments, obstacles, and potential of SACs for photocatalytic CO2 reduction. And further, discusses the principle of photocatalytic carbon dioxide reduction. This work has compared and analyzed the effects of support materials and active site types in SACs on photocatalytic CO2 reduction performance. This work believes that by sharing these developments, some inspiration for the rational design and development of stable and effective photocatalytic CO2 reduction catalysts based on SACs can be provided.

Design and Synthesis of Noble Metal-Based Alloy Electrocatalysts and Their Application in Hydrogen Evolution Reaction.

Hydrogen energy is regarded as the ultimate energy source for future human society, and the preparation of hydrogen from water electrolysis is recognized as the most ideal way. One of the key factors to achieve large-scale hydrogen production by water splitting is the availability of highly active and stable electrocatalysts. Although non-precious metal electrocatalysts have made great strides in recent years, the best hydrogen evolution reaction (HER) electrocatalysts are still based on noble metals. Therefore, it is particularly important to improve the overall activity of the electrocatalysts while reducing the noble metals load. Alloying strategies can shoulder the burden of optimizing electrocatalysts cost and improving electrocatalysts performance. With this in mind, recent work on the application of noble metal-based alloy electrocatalysts in the field of hydrogen production from water electrolysis is summarized. In this review, first, the mechanism of HER is described; then, the current development of synthesis methods for alloy electrocatalysts is presented; finally, an example analysis of practical application studies on alloy electrocatalysts in hydrogen production is presented. In addition, at the end of this review, the prospects, opportunities, and challenges facing noble metal-based alloy electrocatalysts are tried to discuss.

Ru/Ir-Based Electrocatalysts for Oxygen Evolution Reaction in Acidic Conditions: From Mechanisms, Optimizations to Challenges.

The generation of green hydrogen by water splitting is identified as a key strategic energy technology, and proton exchange membrane water electrolysis (PEMWE) is one of the desirable technologies for converting renewable energy sources into hydrogen. However, the harsh anode environment of PEMWE and the oxygen evolution reaction (OER) involving four-electron transfer result in a large overpotential, which limits the overall efficiency of hydrogen production, and thus efficient electrocatalysts are needed to overcome the high overpotential and slow kinetic process. In recent years, noble metal-based electrocatalysts (e.g., Ru/Ir-based metal/oxide electrocatalysts) have received much attention due to their unique catalytic properties, and have already become the dominant electrocatalysts for the acidic OER process and are applied in commercial PEMWE devices. However, these noble metal-based electrocatalysts still face the thorny problem of conflicting performance and cost. In this review, first, noble metal Ru/Ir-based OER electrocatalysts are briefly classified according to their forms of existence, and the OER catalytic mechanisms are outlined. Then, the focus is on summarizing the improvement strategies of Ru/Ir-based OER electrocatalysts with respect to their activity and stability over recent years. Finally, the challenges and development prospects of noble metal-based OER electrocatalysts are discussed.