2D metal nanomaterials offer exciting prospects in terms of their properties and functions. However, the ambient aqueous synthesis of atomically‐thin, 2D metallic nanomaterials represents a significant challenge. Herein, freestanding and atomically‐thin gold nanosheets with a thickness of only 0.47 nm (two atomic layers thick) are synthesized via a one‐step aqueous approach at 20 °C, using methyl orange as a confining agent. Owing to the high surface‐area‐to‐volume ratio, abundance of unsaturated atoms exposed on the surface and large interfacial areas arising from their ultrathin 2D nature, the as‐prepared Au nanosheets demonstrate excellent catalysis performance in the model reaction of 4‐nitrophenol reduction, and remarkable peroxidase‐mimicking activity, which enables a highly sensitive colorimetric sensing of H₂O₂ with a detection limit of 0.11 × 10⁻⁶ m. This work represents the first fabrication of freestanding 2D gold with a sub‐nanometer thickness, opens up an innovative pathway toward atomically‐thin metal nanomaterials that can serve as model systems for inspiring fundamental advances in materials science, and holds potential across a wide region of applications.

Monolayers of assembled nano-objects with a controlled degree of disorder hold interest in many optical applications, including photovoltaics, light emission, sensing, and structural coloration.

We present the characterization of the CTAB-oleate controlled synthesis of gold nanorods (AuNRs). Concentrations of key compounds in the synthetic system were varied in the presence of oleate, including HCl, borohydride, silver nitrate, and ascorbic acid. The longitudinal surface plasmon resonance peak was sensitive to changes in all concentrations. Reducing the concentration of Ag ions below 66 μM led to slower reaction kinetics and incomplete Au reduction. Variation of the ascorbic acid concentration revealed that oleate is responsible for around 44% of reduction of Au³⁺ to Au⁺ before nucleation in these experiments. Increasing the oleate concentration significantly slows the growth kinetics and leads to much longer synthesis times of above 12 h for reaction completion. These observations will enable the design of better methods of synthesizing of AuNRs using binary surfactants.

The ability to synthesize plasmonic nanomaterials with well‐defined structures and tailorable size is crucial for exploring their potential applications. Gold nanoplates (AuNPLs) exhibit appealing structural and optical properties, yet their applications are limited by difficulties in thickness control. Other challenges include a narrow range of tunability in size and surface plasmon resonance, combined with a synthesis conventionally involving cytotoxic cetyltrimethylammonium (CTA) halide surfactant. Here, a one‐step, high‐yield synthesis of single‐crystalline AuNPLs is developed, based on the combined use of two structure‐directing agents, methyl orange and FeBr₃, which undergo preferential adsorption onto different crystalline facets of gold. The obtained AuNPLs feature high shape homogeneity that enables mesoscopic self‐assembly, broad‐range tunability of dimensions (controlled thickness from ≈7 to ≈20 nm, accompanied by modulation of the edge length from ≈150 nm to ≈2 µm) and plasmonic properties. These merits, coupled with a preparation free of CTA‐halide surfactants, have facilitated the exploration of various uses, especially in bio‐related areas. For example, they are demonstrated as biocompatible photothermal agents for cell ablation in NIR I and NIR II windows. This work paves the way to the innovative fabrication of anisotropic plasmonic nanomaterials with desired attributes for wide‐ranging practical applications.