Water adsorption-driven heat transfer (AHT) technology has emerged as a promising solution to address crisis of the global energy consumption and environmental pollution of current heating and cooling processes. Hydrophilicity of water adsorbents plays a decisive role in these applications. This work reports an easy, green, and inexpensive approach to tuning the hydrophilicity of metal-organic frameworks (MOFs) by incorporating mixed linkers, isophthalic acid (IPA), and 3,5-pyridinedicarboxylic acid (PYDC), with various ratios in a series of Al−xIPA-(100−x)PYDC (x: feeding ratio of IPA) MOFs. The designed mixed-linkers MOFs show a variation of hydrophilicity along the fraction of the linkers. Representative compounds with a proportional mixed linker ratio denoted as KMF-2, exhibit an S-shaped isotherm, an excellent coefficient of performance of 0.75 (cooling) and 1.66 (heating) achieved with low driving temperature below 70 °C which offers capability to employ solar or industrial waste heat, remarkable volumetric specific energy capacity (235 kWh m −3 ) and heat-storage capacity (330 kWh m −3 ). The superiority of KMF-2 to IPA or PYDC-containing single-linker MOFs (CAU-10-H and CAU-10pydc, respectively) and most of benchmark adsorbents illustrate the effectiveness of the mixed-linker strategy to design AHT adsorbents with promising performance.

A series of Al-based isomorphs (CAU-10H, MIL-160, KMF-1, and CAU-10pydc) were synthesized using isophthalic acid (ipa), 2,5-furandicarboxylic acid (fdc), 2,5-pyrrole dicarboxylic acid (pyrdc), and 3,5-pyridinedicarboxylic acid (pydc), respectively. These isomorphs were systematically investigated to identify the best adsorbent for effectively separating C2H6/C2H4. All CAU-10 isomorphs exhibited preferential adsorption of C2H6 over that of C2H4 in mixture. CAU-10pydc exhibited the best C2H6/C2H4 selectivity (1.68) and the highest C2H6 uptake (3.97 mmol g–1) at 298 K and 1 bar. In the breakthrough experiment using CAU-10pydc, 1/1 (v/v) and 1/15 (v/v) C2H6/C2H4 gas mixtures were successfully separated into high-purity C2H4 (>99.95%), with remarkable productivities of 14.0 LSTP kg–1 and 32.0 LSTP kg–1, respectively, at 298 K. Molecular simulations revealed that the exceptional separation performance of CAU-10pydc originated from the increased porosity and reduced electron density of the pyridine ring of pydc, leading to a relatively larger decrease in π–π interactions with C2H4 than in the C–H···π interactions with C2H6. This study demonstrates that the pore size and geometry of the CAU-10 platform are modulated by the inclusion of heteroatom-containing benzene dicarboxylate or heterocyclic rings of dicarboxylate-based organic linkers, thereby fine-tuning the C2H6/C2H4 separation ability. CAU-10pydc was determined to be an optimum adsorbent for this challenging separation.

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