continually intensified and could be out of control. Therefore, it is urgent to greatly reduce the gigantic consumption of carbonbased fossil fuels, [1,2] which emit substantial greenhouse gases and tremendously aggravate global warming. Furthermore, it is of great significance to realize carbon neutrality in human society via replacing fossil fuels with low-carbon/carbon-free alternatives. Thus, the conversion of renewable solar energy [3][4][5] into clean and carbonfree hydrogen (H 2 ) fuel is highly attractive. Such a solar-to-H 2 (STH) conversion can be achieved utilizing photocatalytic H 2 evolution via water splitting, [6][7][8][9][10] which is regarded as an alluring, environmentally benign and low-cost strategy. Hence, a highly active, robust, and affordable photocatalyst is the most sought after. [11][12][13] The rational design and synthesis of such a photocatalyst require not only the emerging nanosized building blocks with desired features, but also efficient charge dissociation/ transfer boosted by the strong built-in electric field in a favorable junction system.In the past decades, 2D materials have demonstrated great capacity to achieve efficient and cost-effective photocatalysis for various reactions, due to their distinct physicochemical features. [14][15][16][17][18][19][20][21] Recently, an emerging 2D material, FePS 3 (FPS), [22][23][24][25][26][27] has displayed numerous attractive characteristics for catalysis: i) Ultrathin structure facilitating rapid bulkto-surface electron-hole transport; ii) high specific surface area accelerating efficient adsorption/desorption of reactant and product, and benefiting the anchoring of other nanobuilding blocks; iii) exposed under-coordinated edge atoms serving as active sites to advance the reactions; iv) thicknessdependent electronic band structure promoting the regulation of light absorption and redox abilities of charge carriers; v) p-type semiconductor nature favoring the construction of certain junction system with a strong built-in electric field. Albeit the above alluring advantages, [28][29][30] only a few works reported the application of FPS in photocatalysis. For instance, FPS quantum sheets show the photocatalytic H 2 -evolution rate of 290 µmol h −1 g −1 in 10% triethanolamine aqueous solution under xenon light illumination. [28] Porous FPS nanosheets exhibit the photocatalytic H 2 -evolution activity of 305.6 µmol h −1 g −1 in 10% triethylamine aqueous solution with xenon light irradiation. [29] Nevertheless, to the best of our The aggravating extreme climate changes and natural disasters stimulate the exploration of low-carbon/zero-carbon alternatives to traditional carbonbased fossil fuels. Solar-to-hydrogen (STH) transformation is considered as appealing route to convert renewable solar energy into carbon-free hydrogen. Restricted by the low efficiency and high cost of noble metal cocatalysts, high-performance and cost-effective photocatalysts are required to realize the realistic STH transformation. Herein, the 2D FePS 3 (FPS) nanoshee...