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Electrocatalytic CO2 reduction (ECR) powered by renewable electricity has attracted of wide attention because of its advantages to produce high‐value‐added chemicals and fuels. Additionally, ECR played a crucial role in addressing the challenge of excessive fossil fuel consumption caused by global warming. Herein, a unique armor structure with Ni nanoparticles coated by a carbon shell containing Ni─N─C (Ni─NP@Ni─SA) for industrial ECR to CO in pH‐universal electrolytes is designed. Ni─NP@Ni─SA catalyst exhibits ≈100% CO Faradaic efficiency, and CO partial current density can reach 500, 361, and 615 mA cm−2 in strong alkaline (pH 14), neutral (pH 7.2) and strong acidic (pH 1) electrolytes, respectively. Moreover, Ni─NP@Ni─SA can drive the rechargeable Zn‐CO2 battery with a high power density of 3.45 mW cm−2, and outstanding stability over 36 h. The structural characterizations and theoretical calculation together present that the electron penetration effect of Ni─NP@Ni─SA can strengthen the electronic enrichment state of Ni single atom, which facilitates the reaction kinetics of ECR by decreasing the formation energy barrier of key intermediate *COOH. This work pioneers a new design strategy to enhance the activity of single‐atom catalysts and seek high‐efficiency electrocatalysts for ECR in pH‐universal electrolytes. [ABSTRACT FROM AUTHOR]

Binary single‐atom catalysts (BSACs) have demonstrated fascinating activities compared to single atom catalysts (SACs) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Notably, Fe SACs is one of the most promising ORR electrocatalysts, and further revealing the synergistic effects between Fe and other 3d transition metals (M) for FeM BSACs are very important to enhance bifunctional performance. Herein, density functional theory (DFT) calculations are first adapted to demonstrate the role of various transition metals on the bifunctional activity of Fe sites, and a notable volcano relationship is established through the generally accepted adsorption free energy that ΔG*OH for ORR, and ΔG*O−ΔG*OH for OER, respectively. Further, ten of the atomically dispersed FeM anchored on nitrogen‐carbon support (FeM‐NC) are successfully synthesized with typical atomic dispersion by a facile movable type printing method. The experimental data confirms the bifunctional activity diversity of FeM‐NC between the early‐ and late‐ transition metals, agrees very well with the DFT results. More importantly, the optimal FeCu‐NC shows the expected performance with high ORR and OER activity, thereby, the assembled rechargeable zinc–air battery delivers a high power density of 231 mW cm−2, and an impressive stability that can be stably operated over 300 h. [ABSTRACT FROM AUTHOR]

As a carbon‐free energy carrier, hydrogen has become the pivot for future clean energy, while efficient hydrogen production and combustion still require precious metal‐based catalysts. Single‐atom catalysts (SACs) with high atomic utilization open up a desirable perspective for the scale applications of precious metals, but the general and facile preparation of various precious metal‐based SACs remains challenging. Herein, a general movable printing method has been developed to synthesize various precious metal‐based SACs, such as Pd, Pt, Rh, Ir, and Ru, and the features of highly dispersed single atoms with nitrogen coordination have been identified by comprehensive characterizations. More importantly, the synthesized Pt‐ and Ru‐based SACs exhibit much higher activities than their corresponding nanoparticle counterparts for hydrogen oxidation reaction and hydrogen evolution reaction (HER). In addition, the Pd‐based SAC delivers an excellent activity for photocatalytic hydrogen evolution. Especially for the superior mass activity of Ru‐based SACs toward HER, density functional theory calculations confirmed that the adsorption of the hydrogen atom has a significant effect on the spin state and electronic structure of the catalysts. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) is the heart of many new energy conversions and storage devices, such as metal‐air batteries and fuel cells. However, ORR is currently facing the dilemma of sluggish intrinsic kinetics and the noble electrocatalysts of high price and low reserves. In this work, isolated Co atoms anchored on defective nitrogen‐doped carbon graphene single‐atom catalyst (Co‐SAC/NC) are synthesized via the proposed movable type printing method. The prepared Co‐SAC/NC catalyst demonstrates admirable ORR performance, with a high half‐wave potential of 0.884 V in alkaline electrolytes and outstanding durability. In addition, an assembled zinc–air battery with prepared Co‐SAC/NC as air‐cathode catalyst displays a high‐peak power density of 179 mW cm−2 and a high‐specific capacity (757 mAh g−1). Density functional theory calculations confirm that the true active sites of the prepared catalyst are Co‐N4 moieties, and further reveal a significantly electronic structure evolution of Co sites in the ORR process, in which the project density of states and local magnetic moment of Co atom varies during its whole reaction process. This work not only paves a new avenue for synthesizing SACs as robust electrocatalysts, but also provides an electronic‐level insight into the evolution of the electronic structure of single‐atom catalysts. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The direct oxidation of methane (CH4) into high‐valued C1 oxygenates production has garnered increased attention in effectively using vast CH4 and alleviating the global energy crisis. However, due to the high cleavage energy of C—H bond and low polarity of CH4 molecule, it is difficult to activate the first C—H bond. Furthermore, C1 oxygenates are readily inclined to be oxidized to CO2, because their weaker C—H bond comparing with CH4 molecule, resulting in poor selectivity. Herein, we designed ultrathin PdxAuy alloy NWs supported on ZSM‐5 (Z‐5) to investigate the direct oxidation of CH4 to high value‐added oxygenate under mild conditions. By precisely adjusting the molar ratio of Pd/Au and alloying degree, Pd9Au1NWs/Z‐5 showed an excellent yield of 11.57 mmol·g–l·h–1 and the outstanding selectivity of 95.1% for C1 oxygenates (CH3OH, CH3OOH and HCOOH). The in‐situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd9Au1NWs/Z‐5 was ascribed to the stable one‐dimensional nanostructure and the strong synergy effect with high alloying PdAu, which could increase the adsorption capacity of CH4 molecules on Pd atoms to promote the CH4 conversion. This work offers valuable insights into the design concept of high‐efficient catalysts and the structure‐activity relationship for the direct oxidation of CH4. [ABSTRACT FROM AUTHOR]