Electrocatalytic nitrogen reduction reaction (NRR) is a promising process relative to energy‐intensive Haber–Bosch process. While conventional electrocatalysts underperform with sluggish paths, achieving dissociation of N2 brings the key challenge for enhancing NRR. This study proposes an effective surface chalcogenation strategy to improve the NRR performance of pristine metal nanocrystals (NCs). Surprisingly, the NH3 yield and Faraday efficiency (FE) (175.6 ± 23.6 mg h–1 g–1Rh and 13.3 ± 0.4%) of Rh‐Se NCs is significantly enhanced by 16 and 15 times, respectively. Detailed investigations show that the superior activity and high FE are attributed to the effect of surface chalcogenation, which not only can decrease the apparent activation energy, but also inhibit the occurrence of the hydrogen evolution reaction (HER) process. Theoretical calculations reveal that the strong interface strain effect within core@shell system induces a critical redox inversion, resulting in a rather low valence state of Rh and Se surface sites. Such strong correlation indicates an efficient electron‐transfer minimizing NRR barrier. Significantly, the surface chalcogenation strategy is general, which can extend to create other NRR metal electrocatalysts with enhanced performance. This strategy open a new avenue for future NH3 production for breakthrough in the bottleneck of NRR.

Unlike the well‐established shape/composition control, surface distortion is a newly emerged yet largely unexplored nanosurface engineering for boosting electrocatalysis. Tapping into the novel electrocatalysts for taking full use of the distortion effect is therefore of importance but remains a formidable challenge. Here, an approach to designing highly distorted porous Pt nanosheets (NSs) by electrochemical erosion of ultrathin PtTe2 NSs is reported. The inherent ultrathin feature and massive leaching of Te have conspired to produce a highly distorted structure. As a result, the generated Pt NSs exhibit a much‐enhanced oxygen reduction reaction (ORR) mass and specific activity of 2.07 A mgPt−1 and 3.1 mA cm−2 at 0.90 V versus reversible hydrogen electrode, 9.8 and 10.7 times higher than those of commercial Pt/C. The highly distorted Pt NSs can endure 30 000 cycles with negligible activity decay and structure variation. Density functional theory calculations reveal that the electrochemical corrosion induced nanopores, boundaries, and vacancies consist of Pt sites with substantially low coordination numbers deviating from the one of pristine Pt (111) surface. These Pt sites actively act as electron‐depleting centers for highly efficient electron transfer toward the adsorbing O‐species. This study opens a new design for fully using the distortion effect to promote ORR performance and beyond.

Searching for highly efficient oxygen reduction reaction (ORR) electrocatalysts for fuel cell technology, in which the crystal structure plays a powerful role in regulating the electrocatalysis, is urgent yet challenging. Herein, we have explored the active and stable Pd–Se alloy electrocatalysts with controlled phase toward alkaline ORR. The phase-controlled Pd–Se nanoparticles (NPs) show interesting phase-dependent electrocatalytic performance, in which the Pd17Se15 NPs/C exhibits much better ORR performance than its counterpart, Pd7Se4 NPs/C, and the commercial Pd/C and Pt/C. Based on the detailed analysis, Pd in Pd17Se15 possesses more Se atom coordination and a higher valence state, thus providing a stronger capacity for the absorption of oxygenated species. DFT further reveals more charge transfer from the Pd17Se15 surface to the *OOH intermediate, which is the reason for the activity enhancement.

Direct H2O2 synthesis (DHS) from H2 and O2 is a promising process in industry; however, challenges related to poor H2O2 selectivity and low H2O2 yield remain. We report here that Pd x Pb nanorings (NRs) can serve as high-efficiency catalysts for DHS. We demonstrate that the preferential location of Pb species at the edge and corner can significantly decrease the amount of low-coordinated Pd atoms in Pd x Pb NRs, leading to an enhanced H2O2 yield and selectivity but a reduced degradation rate. Consequently, the optimized catalyst gives a H2O2 yield of 170.1 mol kgcat –1 h–1, being one of the best catalysts reported for DHS to the best of our knowledge. Theoretical calculations reveal that Pd x Pb NRs are favorable for *OOH formation, a key intermediate for DHS, while Pd NRs tend to dissociate O2 to form H2O in the presence of H2. On the other hand, the cleavage of O–O in H2O2 is strongly suppressed on Pd x Pb NRs, leading to a low H2O2 degradation rate. This work highlights the significance of catalyst surface modifications, especially the control of Pd coordination environment on DHS performance, which may provide deep insight for catalyst design in heterogeneous catalysis.