Atomically Dispersed Fe/N4 and Ni/N4 Sites on Separate-Sides of Porous Carbon Nanosheets with Janus Structure for Selective Oxygen Electrocatalysis.

Dual single atoms catalysts have promising application in bifunctional electrocatalysis due to their synergistic effect. However, how to balance the competition between rate-limiting steps (RDSs) of reversible oxygen reduction and oxygen evolution reaction (OER) and fully expose the active centers by reasonable structure design remain enormous challenges. Herein, Fe/N4 and Ni/N4 sites separated on different sides of the carbon nanosheets with Janus structure (FeNijns /NC) is synthesized by layer-by-layer assembly method. Experiments and calculations reveal that the side of Fe/N4 is beneficial to oxygen reduction reaction (ORR) and the Ni/N4 side is preferred to OER. Such Janus structure can take full advantage of two separate-sides of carbon nanosheets and balance the competition of RDSs during ORR and OER. FeNijns /NC possesses superior ORR and OER activity with ORR half-wave potential of 0.92 V and OER overpotential of 440 mV at J = 10 mA cm-2 . Benefiting from the excellent bifunctional activities, FeNijns /NC assembled aqueous Zn-air battery (ZAB) demonstrates better maximum power density, and long-term stability (140 h) than Pt/C+RuO2 catalyst. It also reveals superior flexibility and stability in solid-state ZAB. This work brings a novel perspective for rational design and understanding of the catalytic mechanisms of dual single atom catalysts.

Amine-Triggered Dopamine Polymerization: From Aqueous Solution to Organic Solvents.

Dopamine (DA) polymerization has received significant attention in many fields, however, almost all of the works are limited to aqueous solution and hamper its wide application. This paper reports that amines can trigger DA polymerization by capturing the H+ from DA hydrochloride and intermediates to accelerate the generation of radical species in water or organic solvents. Increasing concentration and decreasing pKb of amines cause the reaction equilibrium to shift toward the product polydopamine (PDA). Water-soluble and easily-removable Na2 SO4 nanowires and NaCl cubes can be used as templates to prepare different morphologies of hollow PDA structures by DA polymerization in ethanol solution. The carbonization production of PDA nanotubes at 900 °C (PDNC-900) is obtained and demonstrates electrochemical activity in the oxygen reduction reaction that is comparable to that of Pt/C.

Sequentially photocatalytic degradation of mussel-inspired polydopamine: From nanoscale disassembly to effective mineralization.

Mussel-inspired polydopamine (PDA) coating has been utilized extensively as versatile deposition strategies that can functionalize surfaces of virtually all substrates. However, the strong adhesion, stability and intermolecular interaction of PDA make it inefficient in certain applications. Herein, a green and efficient photocatalytic method was reported to remove adhesion and degrade PDA by using TiO2-H2O2 as photocatalyst. The photodegradation process of the PDA spheres was first undergone nanoscale disassembly to form soluble PDA oligomers or well-dispersed nanoparticles. Most of the disassembled PDA can be photodegraded and finally mineralized to CO2 and H2O. Various PDA coated templates and PDA hollow structures can be photodegraded by this strategy. Such process provides a practical strategy for constructing the patterned and gradient surfaces by the "top-down" method under the control of light scope and intensity. This sequential degradation strategy is beneficial to achieve the decomposition of highly crosslinked polymers.

Breaking the scaling relations of effective CO2 electrochemical reduction in diatomic catalysts by adjusting the flow direction of intermediate structures.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) is a promising approach to achieving a sustainable carbon cycle. Recently, diatomic catalysts (DACs) have demonstrated advantages in the CO2RR due to their complex and flexible active sites. However, our understanding of how DACs break the scaling relationship remains insufficient. Here, we investigate the CO2RR of 465 kinds of graphene-based DACs (M1M2-N6@Gra) formed from 30 metal atoms through high-throughput density functional theory (DFT) calculations. We find that the intermediates *COOH, *CO, and *CHO have multiple adsorption states, with 11 structural flow directions from *CO to *CHO. Four of these structural flow directions have catalysts that can break the linear scale relationship. Based on the adsorption energy relationship between *COOH, *CHO and *CO, we propose the concepts of linear scaling, moderate breaking, and severe deviation regions, leading to the establishment of new descriptors that identify 14 catalysts with potential superior performance. Among them, ZnRu-N6@Gra and CrNi-N6@Gra can reduce CO2 to CH4 at a low limiting potential. We also discovered that DACs have independent bidirectional electron transfer channels during the adsorption and activation of CO2, which can significantly improve the flexibility and efficiency of regulating the electronic structure. Furthermore, through machine learning (ML) analysis, we identify electronegativity, atomic number, and d electron count as key determinants of catalyst stability. This work provides new insights into the understanding of the DAC catalytic mechanism, as well as the design and screening of catalysts.

Isolated Binary Fe-Ni Metal-Nitrogen Sites Anchored on Porous Carbon Nanosheets for Efficient Oxygen Electrocatalysis through High-Temperature Gas-Migration Strategy.

Atomically dispersed dual-site catalysts can regulate multiple reaction processes and provide synergistic functions based on diverse molecules and their interfaces. However, how to synthesize and stabilize dual-site single-atom catalysts (DACs) is confronted with challenges. Herein, we report a facile high-temperature gas-migration strategy to synthesize Fe-Ni DACs on nitrogen-doped carbon nanosheets (FeNiSAs/NC). FeNiSAs/NC exhibits a high half-wave potential (0.88 V) for the oxygen reduction reaction (ORR) and a low overpotential of 410 mV at 10 mA cm-2 for the oxygen evolution reaction (OER). As an air electrode for Zn-air batteries (ZABs), it shows better performances in aqueous ZABs and excellent stability and flexibility in solid-state ZABs. The high specific surface area (1687.32 m2/g) of FeNiSAs/NC is conducive to electron transport. Density functional theory (DFT) reveals that the Fe sites are the active center, and Ni sites can significantly optimize the free energy of the oxygen-containing intermediate state on Fe sites, contributing to the improvement of ORR and the corresponding OER activities. This work can provide guidance for the rational design of DACs and understand the structure-activity relationship of SACs with multiple active sites for electrocatalytic energy conversion.

Single-atom Zn with nitrogen defects on biomimetic 3D carbon nanotubes for bifunctional oxygen electrocatalysis.

Single atoms catalysts (SACs) have promising development in electrocatalytic energy conversion. Nevertheless, rational design SACs with reversible oxygen electrocatalysis still remain challenge. Herein, we synthesized atomically dispersed Zn with N defect on three-dimensional (3D) biomimetic carbon nanotubes by secondary pyrolysis (Zn-N-C-2), which possesses excellent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalytic activities. The biomimetic 3D structure and unique "leaf-branch" system are beneficial to fully expose the active sites. Density functional theory (DFT) calculations show that Zn-N3-D can optimize the charge distribution and facilitate electron transfer step of OH*→O*. Zn-N-C-2 exhibits higher ORR activity than commercial Pt/C with a half-wave potential (E1/2) of 0.85 V and OER overpotential of 450 mV at 10 mA cm-2. After being assembled into the air cathode of aqueous Zn-air battery (ZAB), it demonstrates superior performances with long-term charge and discharge for more than 200 h. This work not only clarifies the controlled synthesis of N-defects Zn SACs with excellent bifunctional electrocatalyst, but also provide in-depth understanding of structural-performance relationships by regulating local microenvironments.