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Abstract Trigonal planar M3(O/OH) trimers are among the most important clusters in inorganic chemistry and are the foundational features of multiple high‐impact MOF platforms. Here we introduce a concept called isoreticular cluster series and demonstrate that M3(O/OH), as the first member of a supertrimer series, can be combined with a higher hierarchical member (double‐deck trimer here) to advance isoreticular chemistry. We report here an isoreticular series of pore‐space‐partitioned MOFs called M3M6pacsmade from co‐assembly between M3single‐deck trimer and M3x2double‐deck trimer. Important factors were identified on this multi‐modular MOF platform to guide optimization of each module, which enables the phase selection of M3M6pacsby overcoming the formation of previously‐always‐observed same‐cluster phases. The newpacsmaterials exhibit high surface area and high uptake capacity for CO2and small hydrocarbons, as well as selective adsorption properties relevant to separation of industrially important mixtures such as C2H2/CO2and C2H2/C2H4. Furthermore, new M3M6pacsmaterials show electrocatalytic properties with high activity.
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Towards addressing environmental challenges: rational design of metal-organic frameworks-based photocatalysts via a microdroplet approach
Abstract Metal-organic frameworks (MOFs) have attracted much attention in the past decades owing to their amazing properties, including rich surface chemistry, flexible structure, superior surface area, and tunable porosity. MOFs are conventionally synthesized via wet-chemistry methods, which, however, are oftentimes plagued by long reaction durations, inhomogeneous mixing, and limited batch processes. This article reviews a rapid microdroplet-based nanomanufacturing process to fabricate MOFs-based functional materials with controlled hierarchical nanostructures to overcome the aforementioned disadvantages of wet-chemistry processes. The general formation pathways of MOFs inside the microdroplets were investigated by both experimental and theoretical approaches. Further, strategies to integrate MOFs with semiconductors to form hybrid photocatalysts are also summarized towards addressing environmental challenges, with a major focus on CO2photoreduction. The quantitative mechanisms of CO2adsorption, activation, and charge transfer within the hybrid nanostructures were explored by variousin-situtechniques, such as diffuse reflectance infrared Fourier transform spectroscopy, photoluminescence spectroscopy, and x-ray photoelectron spectroscopy. This review provides a new avenue for the rational design of MOFs-based functional materials to tackle a variety of environmental issues, including but not limited to global warming, air pollution, and water contamination.
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- Award ID(s):
- 1727553
- PAR ID:
- 10361857
- Publisher / Repository:
- IOP Publishing
- Date Published:
- Journal Name:
- Journal of Physics: Energy
- Volume:
- 3
- Issue:
- 3
- ISSN:
- 2515-7655
- Page Range / eLocation ID:
- Article No. 032005
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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