Xiao-Qin Liu

Fabrication of magnetically responsive HKUST-1/Fe3O4 composites by dry gel conversion for deep desulfurization and denitrogenation.

Selective adsorption by use of metal-organic frameworks (MOFs) is an effective method for purification of hydrocarbon fuels. In consideration that the adsorption processes proceed in liquid phases, separation and recycling of adsorbents should be greatly facilitated if MOFs were endowed with magnetism. In the present study, we reported for the first time a dry gel conversion (DGC) strategy to fabricate magnetically responsive MOFs as adsorbents for deep desulfurization and denitrogenation. The solvent is separated from the solid materials in the DGC strategy, and vapor is generated at elevated temperatures to induce the growth of MOFs around magnetic Fe3O4 nanoparticles. This strategy can greatly simplify the complicated procedures of the well-known layer-by-layer method and avoid the blockage of pores confronted by introducing magnetic Fe3O4 nanoparticles to the pores of MOFs. Our results show that the adsorbents are capable of efficiently removing aromatic sulfur and nitrogen compounds from model fuels, for example removing 0.62mmolg-1S and 0.89mmolg-1N of thiophene and indole, respectively. In addition, the adsorbents are facile to separate from liquid phases by use of an external field. After 6 cycles, the adsorbents still show a good adsorption capacity that is comparable to the fresh one.

Functionalization of metal–organic frameworks with cuprous sites using vapor-induced selective reduction: efficient adsorbents for deep desulfurization

Functionalization of metal–organic frameworks (MOFs) with Cu(I) sites is extremely desirable for various applications including adsorption, catalysis, and sensing. The traditional method for the conversion of supported Cu(II) to Cu(I) is high-temperature autoreduction (HTA), which produces Cu(I) with an unsatisfactory yield (ca. 50%) but requires quite harsh conditions (e.g. 700 °C, 12 h) that are unsuitable for MOFs. Here we report the rational design of an efficient, controllable strategy for the conversion of supported Cu(II) to Cu(I) by using vapor-induced selective reduction (VISR), in which vapors of weak reducing agents (e.g. methanol) diffuse into the pores of MOFs and interact with Cu(II) precursors. This strategy allows the fabrication of Cu(I) sites with a 100% yield without the formation of Cu(0) at much lower temperatures (e.g. 200 °C, 6 h) and subsequently preserves the structure of MOFs well. Due to the abundant Cu(I) sites and high porosity of MOF supports, the obtained materials exhibit excellent performance in adsorptive desulfurization with regard to capacity, selectivity, and recyclability.

Enhancing the hydrostability and catalytic performance of metal–organic frameworks by hybridizing with attapulgite, a natural clay

Metal–organic frameworks (MOFs) have attracted extensive attention due to their large surface area, diverse structures, and tuneable functionality. However, the poor hydrostability of most reported MOFs hinders their practical applications severely. In this paper, we report a strategy to modulate the properties of a typical MOF, namely MOF-5 [Zn4O(BDC)3; BDC = 1,4-benzenedicarboxylate] by hybridizing it with a natural clay (i.e. attapulgite), for the first time. A new kind of hybrid material resulting from the hybridization of the MOF and attapulgite was thus constructed. Our results showed that the hydrostability of the MOF was apparently improved due to the hybridization with attapulgite. The frameworks of MOF-5 were degraded seriously under the humid atmosphere, while the structure of the hybrid materials could be well preserved. We also demonstrated that the hybrid materials were highly active in the heterogeneous Friedel–Crafts alkylation reaction of benzyl bromide with toluene. The conversion of benzyl bromide reached ∼100% under the reaction conditions investigated. More importantly, the catalytic stability of the hybrid materials was significantly enhanced owing to the introduction of attapulgite. The activity could be well recovered with no detectable loss, and the conversion remained at ∼100% at the sixth run, which was apparently higher than that of MOF-5 (27.7% at the sixth run). The excellent hydrostability, catalytic activity, and reusability make the present materials highly promising for utilization as heterogeneous catalysts in practical applications.

Smart adsorbents with reversible photo-regulated molecular switches for selective adsorption and efficient regeneration

Traditional adsorbents with fixed pore surface properties are unlikely to achieve both selective adsorption and efficient desorption, which are extremely desirable in adsorption processes. Here we report a new class of smart adsorbents by introducing photo-responsive azobenzene derivatives to pore interiors of mesoporous silica. The azobenzene molecules are applied as ON-OFF switches for active sites, and are reversibly regulated by UV/visible light irradiation, thus endowing the adsorbents with unprecedented properties to achieve selective adsorption and efficient desorption.

Fabrication of microporous polymers for selective CO2 capture: the significant role of crosslinking and crosslinker length

Owing to their high physicochemical stability, low skeletal density, tailorable surface properties, and high porosity, microporous crosslink polymers are highly promising for selective CO2 capture, separation, and storage. The crosslinking (CL) and crosslinker length (CLL) in a polymer play a quite significant role in enhancing selective CO2 capture. To investigate the role of CL and CLL, polymers with no crosslinking (non-crosslinking, NCL), and small-(SCL), and long-crosslinker lengths (LCL) were successfully fabricated. It is noteworthy that the polymer containing SCL has remarkable CO2 adsorption capacity and selectivity over the polymer with LCL and NCL. High selectivity for CO2 over CH4/N2 was observed in the sequence SCL > LCL > NCL. This indicates that not only CL but CLL is also significantly important in generating highly efficient adsorbents. The adsorption capacity reaches 208.3 mg g−1, which is higher than that of the benchmarks including activated carbon (122.8 mg g−1), and 13X zeolite (180.3 mg g−1), as well as most reported carbon-based adsorbents. The CO2/N2 and CO2/CH4 selectivity reaches 541.4 and 64, respectively. Moreover, excellent recyclability was observed without loss in CO2 adsorption for 10 cycles. Thus, high CO2 capture, excellent selectivity, and high recyclability under energy-saving mild regeneration conditions make microporous polymers a unique adsorbent for selective CO2 capture from flue gas and natural gas.

Controllable construction of metal–organic polyhedra in confined cavities via in situ site-induced assembly

Poor dispersity and low stability are two predominant shortcomings hindering the applications of metal–organic polyhedra (MOPs). The confinement of MOPs in nanoscale cavities of mesoporous matrices is efficient in overcoming both shortcomings, while the improvement of the current double-solvent method is highly expected. Here we develop a facile, controllable strategy to fabricate three MOPs (coordinated from dicopper and carboxylates) in confined cavities via in situ site-induced assembly (SIA), for the first time. The cavities of mesoporous matrix SBA-16 were pre-functionalized with amine sites, which induce in situ assembly of precursors that diffused into cavities. Hence, both the amount and location of MOPs in the mesoporous matrix can be easily controlled. Upon confinement, the dispersity, stability, and catalytic performance (on ring-opening reactions) of MOPs are greatly improved. Moreover, the enhancement of stability makes it possible to observe MOPs using high-resolution transmission electron microscopy (HRTEM) directly.

Incorporation of Cu(II) and its selective reduction to Cu(I) within confined spaces: efficient active sites for CO adsorption

Cu(I)-containing materials have great potential in various applications such as in CO adsorption; however, development of an efficient and controllable method to produce Cu(I) sites remains a significant challenge; herein, a two-step double-solvent (DS) strategy is reported for the first time to fabricate Cu(I) sites in a representative metal–organic framework, MIL-101(Cr); this strategy ensures that both introduction of the Cu(II) precursor and its reduction to Cu(I) occur inside the pores and significantly minimizes the aggregation of Cu species. This is difficult to realize through conventional methods used for Cu(II) introduction (wet impregnation) or reduction (liquid-phase reduction). The two-step DS strategy involves selective reduction of Cu(II) to form Cu(I) without the formation of any Cu(0). The obtained Cu(I)-containing materials exhibit an excellent CO adsorption capacity (up to 2.42 mmol g−1) at 298 K and 1 bar, much better than that of the benchmark adsorbents including CuCl/γ-Al2O3 (1.0 mmol g−1), CuCl/MCM-41 (0.57 mmol g−1), and CuZSM-5 (0.11 mmol g−1).

Calcium oxide-modified mesoporous silica loaded onto ferriferrous oxide core: Magnetically responsive mesoporous solid strong base

The design of new type of solid strong base with ideal activity, stability, and reusability is strongly urged by the growing demand of green chemistry and sustainable development. In this study, a new type of mesoporous solid strong base, denoted as CaO/mSiO2/Fe3O4, is successfully fabricated by successively coating SiO2 onto Fe3O4 magnetic nanoparticles and loading CaO into the mesoporous SiO2. Compared with a series of other typical solid bases, the CaO/mSiO2/Fe3O4 exhibits higher activity towards the synthesis of dimethyl carbonate by the transesterification of ethylene carbonate and methanol. The activity of the CaO/mSiO2/Fe3O4 is not observed to decrease obviously even after sextic catalyst recirculation, and in particular, the recovery of the catalyst without quality loss is very convenient due to the good magnetic responsiveness of the Fe3O4 cores.

Potassium-incorporated mesoporous carbons: strong solid bases with enhanced catalytic activity and stability

With the growing demand for green chemistry, mesoporous solid strong bases have attracted increasing attention in view of their tremendous potential as eco-friendly catalysts in diverse reactions. In the present study, K-incorporated mesoporous carbon is successfully prepared through high-temperature chemical activation combined with the hard-templating method. The combined method is proved to be very effective at promoting the formation of stable K species that strongly interact with the carbon support. The obtained solid bases thus have both high activity and enhanced water-resistant stability, which is reflected in their catalysis of the transesterification of ethylene carbonate with methanol to dimethyl carbonate. A much higher turnover frequency (TOF) value (430.4 h−1) and better reusability are thus observed, compared with a series of typical and popular solid bases, such as MgO (TOF, 1.0 h−1) and CaO/SBA-15 (TOF, 6.4 h−1).