The electrochemical nitrogen reduction reaction (NRR) offers an environmentally benign and sustainable alternative for NH 3 synthesis. Black phosphorus (BP) has a similar valence electron structure to nitrogen, which enables the effective adsorption and activation of N 2 molecules for NRR. BP quantum dots (QDs) have larger specific surface areas and more abundant active centers than BP nanosheets. However, the aggregation and poor conductivity of BPQDs limit their catalytic activity. To solve these problems, we reported the synthesis of BPQDs/Ti 3 C 2 heterostructures which is stabilized by interfacial P−O−Ti bonds. A new low-temperature electrochemical exfoliation method is used to prepare the BPQDs, in order to induce moderate oxygen-containing functional groups on the BPQD surface without damaging the basic structure of BP. The BPQDs/Ti 3 C 2 heterostructures exhibit much enhanced NRR activity compared with pure BPQDs or Ti 3 C 2 electrocatalysts, attributed to the strong interfacial coupling effect. The BPQDs/Ti 3 C 2 could exhibit a high NH 3 yield of 51.6 μg h −1 mg cat.−1 , a Faradaic efficiency of 16.1%, and good durability.

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Few‐layer black phosphorus (BP) is a promising semiconductor with excellent optoelectronic properties. However, the poor stabilization and strong asymmetry between electron and hole transports hinder the application of BP. Doping of heteroatoms is an effective strategy to regulate the electronic structure and stability of BP without sacrificing its unique 2D structure, which is a promising way to tune the physicochemical properties of BP for various applications. In this review, the recent advances in doping engineering of BP are summarized, involving the theoretical prediction of new characteristic for doped BP and the corresponding experimental synthesis methods. The effects of dopant atoms on the structure and performance of BP and its related applications, such as the field‐effect transistors, optoelectronic devices, inverter devices, and catalysis, are also summarized.

Nano black phosphorus (BP) has been widely used in many fields due to its outstanding properties. The novel morphology and structure of nano BP would bring new properties and expand its application. In this work, a novel holey phosphorene was prepared by a low temperature electrochemical exfoliation method for the first time. The low temperature condition plays a significant role in reducing the oxidizing reaction rate, thus facilitating the formation of pore in the basal plane of BP during the exfoliation process. The as‐prepared holey phosphorene can act as a metal‐free electrocatalyst for electroreduction of nitrogen, which exhibits a high NH3 yield of 46.04 μg h−1 mg−1cat. with a Faradaic efficiency of 8.78 % at −0.7 V vs. RHE.