Surface modulation at the atomic level has been an important approach for boosting the performance of electrocatalysts. Here, a combined theoretical and experimental study on Ni atom decorated hierarchical MoS2 nanosheets supported on a multichannel carbon matrix (MCM) is presented. The obtained hybrid [email protected]–Ni electrocatalyst with activated S sites exhibits high performance in electrocatalytic hydrogen evolution. Abstract Surface modulation at the atomic level is an important approach for tuning surface chemistry and boosting the catalytic performance. Here, a surface modulation strategy is demonstrated through the decoration of isolated Ni atoms onto the basal plane of hierarchical MoS2 nanosheets supported on multichannel carbon nanofibers for boosted hydrogen evolution activity. X‐ray absorption fine structure investigation and density functional theory (DFT) calculation reveal that the MoS2 surface decorated with isolated Ni atoms displays highly strengthened H binding. Benefiting from the unique tubular structure and basal plane modulation, the newly developed MoS2 catalyst exhibits excellent hydrogen evolution activity and stability. This single‐atom modification strategy opens up new avenues for tuning the intrinsic catalytic activity toward electrocatalytic water splitting and other energy‐related processes.

Published in: "Advanced Functional Materials".