We report the synthesis of a highly active and stable metal‐organic framework derived Ni‐based catalyst for the photothermal reduction of CO2 to CH4. Through the controlled pyrolysis of MOF‐74 (Ni), the nature of the carbonaceous species and therefore photothermal performance can be tuned. CH4 production rates of 488 mmol g−1 h−1 under UV‐visible‐IR irradiation are achieved when the catalyst is prepared under optimized conditions. No particle aggregation or significant loss of activity were observed after ten consecutive reaction cycles or more than 12 hours under continuous flow configuration. Finally, as a proof‐of‐concept, we performed an outdoor experiment under ambient solar irradiation, demonstrating the potential of our catalyst to reduce CO2 to CH4 using only solar energy.
Nowadays, nanofiltration is widely used for water treatment due to its advantages, such as energy-saving, sustainability, high efficiency, and compact equipment. In the present work, novel nanofiltration membranes based on the polymer of intrinsic microporosity PIM-1 modified by metal-organic frameworks (MOFs)—MIL-140A and MIL-125—were developed to increase nanofiltration efficiency for the removal of heavy metal ions and dyes. The structural and physicochemical properties of the developed PIM-1 and PIM-1/MOFs membranes were studied by the spectroscopic technique (FTIR), microscopic methods (SEM and AFM), and contact angle measurement. Transport properties of the developed PIM-1 and PIM-1/MOFs membranes were evaluated in the nanofiltration of the model and real mixtures containing food dyes and heavy metal ions. It was found that the introduction of MOFs (MIL-140A and MIL-125) led to an increase in membrane permeability. It was demonstrated that the membranes could be used to remove and concentrate the food dyes and heavy metal ions from model and real mixtures.
Conspectus
Conventionally, the virtue of porosity is only
given to porous
solids. Metal Organic Frameworks (MOFs), carbon materials, or zeolites
are some examples. However, processing these solids is not a straightforward
task. Here, we discuss how to endow porous solids (MOFs) with liquid
phase processability. More specifically, we show that surface modification
of MOF crystals can lead to the formation of porous liquids (PLs)
that can be further processed in the liquid phase. For instance, when
placed in mesitylene, ZIF-67 predictably sediments. In contrast, with
the adequate surface modification, stable dispersion of ZIF-67 can
be achieved. Our proposed surface modification is facile and rapid.
N-Heterocyclic carbenes are chosen as modifying agents as they are
similar to imidazole linkers present on ZIFs. A simple stirring of
a MOF and carbene mixture results in a modified solid. The morphology
and textural properties of the modified MOF do not change from the
ones of its parent. Since the porosity in solution remains unoccupied,
the obtained stable colloids behave as porous liquids. Research into
porous liquids is an emerging field that has already shown great promise
in gases storage. Our breakthrough experiments show that these particular
PLs have large potential for the separation of CO2/CH4 mixtures.
The surface functionalized ZIF-67 could also
be coprocessed with
polymers to yield highly loaded Mixed-Matrix Membranes (MMMs) that
cannot be achieved with a pristine MOF. Dispersions of functionalized
ZIF-67 were blended with 6FDA-DAM and other homemade polymers in a
shape of MMMs. While MMMs based on a pure MOF maintain good physical
resistance at low loadings, increasing the concentration of MOF results
in brittle composites. In contrast, MMMs made from functionalized
ZIF retain good mechanical strength even at ca. 47.5 wt % loadings.
Such high loading was possible to achieve due the better dispersion
of the MOF particles during MMM fabrication and to the better affinity
of the modified MOF with the polymer. The results obtained for this
MMM are among the best MMMs ever reported for high challenging C3H6/C3H8 separation.
The method is not limited to ZIF-67 but can be applied to a large
body of MOFs that are constructed from imidazole-based linkers, as
shown in this Account. The factors that determine whether a PL is
formed include, but are not limited to, surface to volume ratio, framework
particle size, and topology. On top of that, we propose potential
strategies for the expansion of this method by carefully choosing
surface modifiers that will suit other families of MOFs.
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