The electronic metal–support interaction (EMSI) plays a crucial role in catalysis as it can induce electron transfer between metal and support, modulate the electronic state of the supported metal, and optimize the reduction of intermediate species. In this work, the tailoring of electronic structure of Pt single atoms supported on N‐doped mesoporous hollow carbon spheres (Pt1/NMHCS) via strong EMSI engineering is reported. The Pt1/NMHCS composite is much more active and stable than the nanoparticle (PtNP) counterpart and commercial 20 wt% Pt/C for catalyzing the electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 40 mV at a current density of 10 mA cm−2, a high mass activity of 2.07 A mg−1Pt at 50 mV overpotential, a large turnover frequency of 20.18 s−1 at 300 mV overpotential, and outstanding durability in acidic electrolyte. Detailed spectroscopic characterizations and theoretical simulations reveal that the strong EMSI effect in a unique N1−Pt1−C2 coordination structure significantly tailors the electronic structure of Pt 5d states, resulting in promoted reduction of adsorbed proton, facilitated H−H coupling, and thus Pt‐like HER activity. This work provides a constructive route for precisely designing single‐Pt‐atom‐based robust electrocatalysts with high HER activity and durability.

Electrochemically converting water into oxygen/hydrogen gas is ideal for high-density renewable energy storage in which robust electrocatalysts for efficient oxygen evolution play crucial roles. To date, however, electrocatalysts with long-term stability have remained elusive. Here we report that single-crystal Co3O4 nanocube underlay with a thin CoO layer results in a high-performance and high-stability electrocatalyst in oxygen evolution reaction. An in situ X-ray diffraction method is developed to observe a strong correlation between the initialization of the oxygen evolution and the formation of active metal oxyhydroxide phase. The lattice of skin layer adapts to the structure of the active phase, which enables a reversible facile structural change that facilitates the chemical reactions without breaking the scaffold of the electrocatalysts. The single-crystal nanocube electrode exhibits stable, continuous oxygen evolution for >1,000 h. This robust stability is attributed to the complementary nature of defect-free single-crystal electrocatalyst and the reversible adapting layer.

Polymeric carbon nitride (CN) is one of the most promising metal-free photocatalysts to alleviate the energy crisis and environmental pollution. Loading cocatalysts is regarded as an effective way to improve the photocatalytic efficiency of CNs. However, commonly used noble metal cocatalysts limit their applications due to their rarity and high cost. Herein, we present the effective synthesis of single-atom copper-modified CN via supramolecular preorganization with subsequent condensation, which provides effective charge transfer pathways by an “infused” delocalized state with variable-valence catalysis at the same time. The C–Cu–N2 single-atom catalytic site can activate CO2 molecules and reduces the energy barrier toward photocatalytic CO2 reduction. Excellent performance for photocatalytic CO2 reduction was found. This work thereby provides a general protocol of designing a noble-metal-free photocatalyst with infused metal centers toward a wide range of applications.

Real bifunctional electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction have to be the ones that exhibit a steady configuration during/after reaction without irreversible structural transformation or surface reconstruction. Otherwise, they can be termed as “precatalysts” rather than real catalysts. Herein, through a strongly atomic metal–support interaction, single-atom dispersed catalysts decorating atomically dispersed Ru onto a nickel–vanadium layered double hydroxide (LDH) scaffold can exhibit excellent HER and OER activities. Both in situ X-ray absorption spectroscopy and operando Raman spectroscopic investigation clarify that the presence of atomic Ru on the surface of nickel–vanadium LDH is playing an imperative role in stabilizing the dangling bond-rich surface and further leads to a reconstruction-free surface. Through strong metal–support interaction provided by nickel–vanadium LDH, the significant interplay can stabilize the reactive atomic Ru site to reach a small fluctuation in oxidation state toward cathodic HER without reconstruction, while the atomic Ru site can stabilize the Ni site to have a greater structural tolerance toward both the bond constriction and structural distortion caused by oxidizing the Ni site during anodic OER and boost the oxidation state increase in the Ni site that contributes to its superior OER performance. Unlike numerous bifunctional catalysts that have suffered from the structural reconstruction/transformation for adapting the HER/OER cycles, the proposed Ru/Ni3V-LDH is characteristic of steady dual reactive sites with the presence of a strong metal–support interaction (i.e., Ru and Ni sites) for individual catalysis in water splitting and is revealed to be termed as a real bifunctional electrocatalyst.

Unraveling the reaction mechanism behind CO2 reduction reaction (CO2RR) is a crucial step for advancing the development of efficient and selective electrocatalyst to yield valuable chemicals. To understand the mechanism...