A new strategy to construct MOF-on-MOF derivatives for the removal of tetracycline hydrochloride from water by activation of peroxymonosulfate.

A MOF-on-MOF composite derivative material named ZIF-67@Ce-MOF-600 was designed and synthesized. The preparation of ZIF-67@Ce-MOF-600 was optimized from the aspects of the ratio of metal and ligand, heat-treatment temperature. It was demonstrated by XRD, FT-IR, SEM-EDS and TEM. The optimum conditions for the activation of PMS by ZIF-67@Ce-MOF-600 for the degradation of tetracycline (TC) were investigated by adjusting the catalyst dosage, TC, pH, peoxymonosulfate (PMS) concentration, and different kinds of water, co-existing anions and pollution. Under optimal conditions (20 mg catalysts and 50 mg PMS added) in 100 mL of tetracyclines (TC) solvent (20 mg TC/L), the removal rate could reach up to 99.2% and after five cycles was 70.5%. The EPR results indicated the presence of free radicals and non-free radical, among which free radicals intended to play a major role in the degradation process. Its possible degradation pathways and attack sites were analyzed by liquid-phase mass spectrometry and DFT analysis.

Precise recognition and efficient recovery of Pd(II) from high-level liquid waste by a novel aminothiazole-functionalized silica-based adsorbent.

Efficient recognition, separation and recovery of palladium from high-level liquid waste (HLLW) not only helps the safe, green and environmentally friendly disposal of nuclear waste, but also is an essential important supplement to overcome the growing shortage of natural palladium resources. Herein, a novel silica-based functional adsorbent named 2AT-SiAaC was prepared by a two-step method, i.e., grafting of 2-aminothiazole (2AT) via the amidated reaction after in-situ polymerization of acrylic monomers on porous silica. SEM, EDS, TG-DSC, BET and PXRD all proved the successful preparation of 2AT-SiAaC, and it exhibited ultrahigh adsorption selectivity for Pd(II) (Kd (distribution coefficient) ≥ 10,344.2 mL/g, SFPd/M (separation factor) ≥ 613.7), fast adsorption kinetics with short equilibrium time (t ≤ 1 h) and good adsorption capacity (Q ≥ 62.1 mg Pd/g). The dynamic column experiments shows that 2AT-SiAaC achieved efficiently separation of Pd(II) from simulated HLLW, and the enrichment coefficients (C/C0) of Pd(II) was as high as about 14 with the recovery rate nearly 99.9% and basically kept the same performance in three adsorption-desorption column cycle experiments. The adsorption mechanism was analyzed by FT-IR, XPS and DFT calculations, and the ultrahigh selectivity of 2AT-SiAaC was attributed to the preferred affinity of the soft N-donor atoms in 2AT for Pd(II). NO3- ions participated in the adsorption reaction to keep charge balance, and the frontier orbital electron density distribution diagram shows the charge transfer in the process of material preparation and adsorption. To sum up, 2AT-SiAaC adsorbent provided a new insight for precise recognition and efficient separation of Pd(II) from HLLW.

Selective separation of cadmium(ii) from zinc(ii) by a novel hydrophobic ionic liquid including an N,N,N',N'-tetrakis(2-methylpyridyl)-1,2-phenylenediamine-4-amido structure: a hard-soft donor combined method.

A novel hydrophobic ionic liquid including an N,N,N',N'-tetrakis(2-methylpyridyl)-1,2-phenylenediamine-4-amido structure ((IL-1,2-tpbd)+NTf2-) was successfully synthesized. (IL-1,2-tpbd)+NTf2- combined one amido (O-hard donor) and four pyridine (N-soft donor) groups. Its Cd2+ and Zn2+ separation behavior in nitric acid solution was investigated as a function of the extraction time, effect of pH etc. by dissolving (IL-1,2-tpbd)+NTf2- in a room temperature ionic liquid, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ((C6mim)+NTf2-). The extraction kinetics were fairly fast and could reach equilibrium within 4 h. When pHeq ≥ 1.8, the extraction percentage of Cd2+ and Zn2+ remained constant and the maximum separation factor was calculated as 12.78 at pHeq = 3.1; when pHeq < 1.8, the extraction percentage of Cd2+ and Zn2+ decreased drastically due to the protonation of the pyridine groups. Complete stripping of the extracted Cd2+ and Zn2+ from the ionic liquid phase into an aqueous phase was successfully achieved under highly acidic conditions ([HNO3] = 2 M) without adding any other metal complex forming agents. The extraction mechanism was summarized as a cation exchange due to the independence of nitrate ions in the extraction process. Additionally, the results of the slope analysis and UV-vis titration revealed the formation of a 1 : 2 complex. Furthermore, (IL-1,2-tpbd)+NTf2- showed a higher preference for Cd2+ even under the interference of various co-existing metal ions.