11 ABSTRACT: Nanofiltration can be a useful tool to remove pharmaceuticals in water 12 sources. The performance of the most used Thin Film Composite (TFC) membranes, 13 typically with a thin polyamide (PA) layer, can be improved using Thin Film 14 Nanocomposite (TFN) membranes obtained by the introduction of a filler within the PA 15 layer. In this work, to control the positioning of the filler two kinds of PA/MOF Bilayered 16 TFC (BTFC) membranes, PA/ZIF-93 and PA/HKUST-1, were synthesized onto polyimide 17 supports. First, the interfacial synthesis was used for the preparation of a MOF layer, and 18 second, a PA layer was synthesized by interfacial polymerization. These BTFC membranes were applied in the nanofiltration of Diclofenac and Naproxen aqueous solutions obtaining 20 a maximum water permeance of 33.1 and 24.9 L·m -2 ·h -1 ·bar -1 , respectively, with a rejection 21 ≥98 % when HKUST-1 was used. These permeance improvements (using Diclofenac, 4.9 22 and 3.4 times the value of the TFC and TFN membranes, respectively) are related to the PA 23 layer thickness, MOF porosity, membrane hydrophilicity and membrane roughness. 24 KEYWORDS: Interfacial synthesis, pharmaceuticals removal, nanofiltration, 25 Polyamide/MOF bilayer, Metal-Organic frameworks 26 INTRODUCTION27 A current environmental problem is the presence of so-called micro-pollutants or emerging 28 contaminants present in wastewater treatment plant (WWTP) effluents, surface water, 29 ground water and even drinking water. WWTPs are not capable of removing these micro-30 pollutants effectively. 1,2 These contaminants include pharmaceuticals, which are not 31 completely assimilated by the organism and end up in the aquatic environment causing 32 negative effects on the human and ecological health. 3,4 For example in effluents of WWTP 33 located in the Ebro River basin, where the University of Zaragoza is placed, Diclofenac and 34 Naproxen were detected up to levels of 1.1 g·L -1 and 1.7 g·L -1 , respectively, the total 35 pharmaceutical concentration being about 0.02 mg·L -1 . 5 Several research studies have 36 examined the use of membrane technologies as effective processes to remove micro-37 pollutants from water. 6,7 38 Nanofiltration has become an interesting membrane separation process in a wide range of 39 fields (pharmaceuticals, 8 food, 9 textile, 10 drinking water, 11 etc.) due to its low consumption 40 of energy and low-cost maintenance in comparison with other separation processes such as distillation 12 or reverse osmosis 13 for both aqueous and organic streams. Thin film 42 composite (TFC) membranes are the most commonly used in this application, consisting of 43 a non-woven fabric at the bottom that gives mechanical stability to the whole ensemble, an 44 asymmetric polymeric support (usually made by phase inversion) and a selective ultrathin 45 film layer at the top, synthesized by interfacial polymerization. 12 46 One way to increase the flux of these membranes without sacrificing rejection is the 47 introduction of nanoparticles...