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[Display omitted] • Metal chloride functionalized MOF-253(Al) was designed and prepared for NH 3 capture and separation. • NH 3 capture capacity of the optimal functionalized MOF is 3.33 times that of the pristine MOF. • Highly selective separation of NH 3 from NH 3 /N 2 /H 2 mixture was achieved. • The excellent performance is ascribed to NH 3 coordination toward Ni2+ and its hydrogen bonding with Cl− and carboxyl. Ammonia (NH 3) is produced from nitrogen (N 2) and hydrogen (H 2) by the Harber-Bosch process at high pressure and high temperature. Due to the reversibility and low conversion efficiency of the reaction, the product contains a large amount of raw gas, which seriously affects the production efficiency of ammonia. Therefore, it is essential to exploit high-performance adsorbents for separating NH 3 from NH 3 /N 2 /H 2 mixtures. Herein, we designed and synthesized a kind of metal–organic framework (MOF) composites by anchoring metal chloride (NiCl 2 , CoCl 2 , or SnCl 2) on the bipyridinium groups in the MOF-253(Al) pores. It is found that the optimal composite shows an NH 3 uptake capacity of 18.0 mmol/g at 25.0 °C and 1.0 bar, which is 3.33 times that of the pristine MOF-253(Al), and the composite exhibits a much faster adsorption kinetics of NH 3 than the pristine MOF-253(Al). Significantly, the excellent NH 3 uptake capacity at low pressure allows selective trapping of NH 3 from NH 3 /N 2 /H 2 at 25.0 °C with the selectivity coefficients of 5708 to N 2 and 2320 to H 2. Spectral measurements reveal that the synergistic action of NH 3 coordination to the metal in the MOF and the hydrogen bonding of NH 3 with both O atoms of the carboxyl groups and Cl− of the guest molecules account for such an excellent capture and selectivity. In general, the strategy developed here is simple and effective for improving the selectivity of NH 3 separation, which opens a new way for the design of high-performance solid adsorbents. [ABSTRACT FROM AUTHOR]

• A pore environment tailoring strategy for COFs was proposed to boost Pd(II) capture. • The adsorbent exhibited a high adsorption capacity for Pd(II) (532 mg/g). • Excellent selectivity, fast kinetics, and good reusability for Pd(II) recovery. • The remarkable performances depended on synergistic multiple interactions. Palladium is a rare resource, and its content in the earth's crust is very low. Thus, its selective recovery from a secondary source is of great importance but a challenging task. Herein, we have constructed a series of bipyridine-based two dimensional (2D) covalent organic frameworks (COFs) TFBBPY-COF, TFBBPY-OH-COF and TFBBPY-OMe-COF, and explored their extraction performance towards palladium in aqueous solutions. It is found that by tailoring the pore environment of these COFs, TFBBPY-OMe-COF shows a highly efficient adsorption and excellent selectivity for palladium recovery, and the maximum sorption capacity is up to 532 mg g−1, which is the highest value among the crystalline porous adsorbents reported up to now. Furthermore, TFBBPY-OMe-COF has been successfully employed to capture Pd(II) with a high selectivity (92.3%) in a simulated solution derived from a waste printed circuit boards. Spectral experiments and theoretical calculations reveal that the excellent adsorption of palladium is mainly attributed to the multiple hydrogen bonds of C–H---Cl and coordination of O and pyridine-N to Pd(II). [ABSTRACT FROM AUTHOR]

• A pore environment tailoring strategy for COFs was proposed to boost Pd(II) capture. • The adsorbent exhibited a high adsorption capacity for Pd(II) (532 mg/g). • Excellent selectivity, fast kinetics, and good reusability for Pd(II) recovery. • The remarkable performances depended on synergistic multiple interactions. Palladium is a rare resource, and its content in the earth's crust is very low. Thus, its selective recovery from a secondary source is of great importance but a challenging task. Herein, we have constructed a series of bipyridine-based two dimensional (2D) covalent organic frameworks (COFs) TFBBPY-COF, TFBBPY-OH-COF and TFBBPY-OMe-COF, and explored their extraction performance towards palladium in aqueous solutions. It is found that by tailoring the pore environment of these COFs, TFBBPY-OMe-COF shows a highly efficient adsorption and excellent selectivity for palladium recovery, and the maximum sorption capacity is up to 532 mg g−1, which is the highest value among the crystalline porous adsorbents reported up to now. Furthermore, TFBBPY-OMe-COF has been successfully employed to capture Pd(II) with a high selectivity (92.3%) in a simulated solution derived from a waste printed circuit boards. Spectral experiments and theoretical calculations reveal that the excellent adsorption of palladium is mainly attributed to the multiple hydrogen bonds of C–H---Cl and coordination of O and pyridine-N to Pd(II). [ABSTRACT FROM AUTHOR]