Novel Porous Organic Polymer Catalyst with Phosphate and Sulfonic Acid Sites for Facile Esterification of Levulinic Acid.

Biomass-derived value-added materials such as levulinic acid (LA) are favorable natural resources for producing ester-based biolubricants owing to their biodegradability, nontoxicity, and excellent metal-adhering properties. However, highly active catalysts must be developed to carry out efficient esterification of LA with aliphatic alcohols, especially long-chain aliphatic alcohols. In this study, we developed a novel porous covalent organic polymer catalyst (BPOP-SO3H) with dual acid sites, phosphate and sulfonic acid sites, for the esterification of LA. The prepared BPOP-SO3H catalyst was verified using various surface analysis techniques. BPOP-SO3H exhibited 98% LA conversion with n-butanol and 99% selectivity for butyl levulinate ester within 30 min, which is superior to that of most reported catalysts. BPOP-SO3H also showed high LA conversion and ester selectivity when other aliphatic alcohols were used. Moreover, BPOP-SO3H showed good recyclability for five consecutive cycles. We believe that incorporating a high density of acid sites into a porous polymer with a large surface area and hierarchical pores is a promising approach for developing heterogeneous acid catalysts for the production of alkyl levulinate esters from LA.

Novel benzylphosphate-based covalent porous organic polymers for the effective capture of rare earth elements from aqueous solutions.

It has been a major challenge to develop stable and cost-effective porous materials that efficiently recover heavy rare earth elements (HREEs) due to ever-increasing demand, low availability and high cost of HREEs. This study presents two novel benzylphosphate-based covalent porous organic polymers (BPOP-1 and BPOP-2) that were prepared by facile one-pot Friedel-Crafts reactions. Various analytical techniques are used to investigate the successful syntheses of BPOP materials and establish their material properties, which include an unusual crystalline nature, large surface area, hierarchical pore structure, and superior chemical stabilities. The BPOPs effectively adsorb, and thus remove HREEs from aqueous media. In particular, BPOP-1 had higher phosphate content and exhibits superior adsorption capacities (Eu3+: 289.5; Gd3+: 292.7; Tb3+: 294.4; Dy3+: 301.9 mg/g) than BPOP-2, while BPOP-2 had higher mesoporosity and correspondingly supports faster adsorption kinetics. Remarkably, both BPOP materials exhibit some of the highest HREE adsorption capacities reported to date, the selective capture of Dy3+ ions, and excellent cyclic adsorption/desorption properties. We provide a potential adsorption mechanism for Dy3+ capture by the BPOP adsorbent. These demonstrate that introducing phosphate functionality into a robust porous polymer backbone with high surface area is a promising strategy for selective HREEs capture from wastewater.

Porous Covalent Organic Polymers Comprising a Phosphite Skeleton for Aqueous Nd(III) Capture.

In order to meet the ever-increasing industrial demand for rare-earth elements (REEs), it is desirable to separate and recycle them at low concentrations from various sources including industrial and urban wastes. Here, we introduced phosphorus binding sites on the hydrophobic surface of a robust and high-surface area porous polymer backbone for environmentally benign and selective recovery of REEs via adsorption. For this purpose, two porous covalent organic polymer (COP) materials incorporated with in-built phosphite functionality (P-COP-1 and P-COP-2) were synthesized and applied for the adsorptive separation of Nd(III) ions from aqueous solution. A strategy to develop a series of P-COPs via a simple Friedel-Crafts reaction was introduced, and their application to the selective adsorption of REEs was explored for the first time. The newly synthesized P-COPs were amorphous and/or weakly crystalline and showed excellent chemical stability and large specific surface area with sufficient mesoporosity for enhanced diffusion of REE ions. P-COP-1 exhibited an exceptionally high Nd(III) adsorption capacity of 321.0 mg/g, corresponding to the stoichiometric ratio of P/Nd(III) = 1:0.7 and high selectivity of >86% over other competing transition and alkaline earth metal ions, whereas P-COP-2 gave a Nd(III) adsorption capacity of 175.6 mg/g at 25 °C and pH 5. Moreover, P-COP-1 showed a distribution coefficient value of 5.45 × 105 mL/g, which is superior to other benchmark adsorbent materials reported so far. Finally, the P-COPs were reusable for a minimum of 10 cycles without deterioration in adsorption capacities.

Selective Adsorption of Rare Earth Elements over Functionalized Cr-MIL-101.

Efficient rare earth elements (REEs) separation and recovery are crucial to meet the ever-increasing demand for REEs extensively used in various high technology devices. Herein, we synthesized a highly stable chromium-based metal-organic framework (MOF) structure, Cr-MIL-101, and its derivatives with different organic functional groups (MIL-101-NH2, MIL-101-ED (ED: ethylenediamine), MIL-101-DETA (DETA: diethylenetriamine), and MIL-101-PMIDA (PMIDA: N-(phosphonomethyl)iminodiacetic acid)) and explored their effectiveness in the separation and recovery of La3+, Ce3+, Nd3+, Sm3+, and Gd3+ in aqueous solutions. The prepared materials were characterized using various analytical instrumentation. These MOFs showed increasing REE adsorption capacities in the sequence MIL-101 < MIL-101-NH2 < MIL-101-ED < MIL-101-DETA < MIL-101-PMIDA. MIL-101-PMIDA showed superior REE adsorption capacities compared to other MOFs, with Gd3+ being the element most efficiently adsorbed by the material. The adsorption of Gd3+ onto MIL-101-PMIDA was examined in detail as a function of the solution pH, initial REE concentration, and contact time. The obtained adsorption equilibrium data were well represented by the Langmuir model, and the kinetics were treated with a pseudo-second-order model. A plausible mechanism for the adsorption of Gd3+ on MIL-101-PMIDA was proposed by considering the surface complexation and electrostatic interaction between the functional groups and Gd3+ ions under different pH conditions. Finally, recycling tests were carried out and demonstrated the higher structural stability of MIL-101-PMIDA during the five adsorption-regeneration runs.

Carbon nanotube/metal-sulfide composite flexible electrodes for high-performance quantum dot-sensitized solar cells and supercapacitors.

Carbon nanotubes (CNT) and metal sulfides have attracted considerable attention owing to their outstanding properties and multiple application areas, such as electrochemical energy conversion and energy storage. Here we describes a cost-effective and facile solution approach to the preparation of metal sulfides (PbS, CuS, CoS, and NiS) grown directly on CNTs, such as CNT/PbS, CNT/CuS, CNT/CoS, and CNT/NiS flexible electrodes for quantum dot-sensitized solar cells (QDSSCs) and supercapacitors (SCs). X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy confirmed that the CNT network was covered with high-purity metal sulfide compounds. QDSSCs equipped with the CNT/NiS counter electrode (CE) showed an impressive energy conversion efficiency (η) of 6.41% and remarkable stability. Interestingly, the assembled symmetric CNT/NiS-based polysulfide SC device exhibited a maximal energy density of 35.39 W h kg-1 and superior cycling durability with 98.39% retention after 1,000 cycles compared to the other CNT/metal-sulfides. The elevated performance of the composites was attributed mainly to the good conductivity, high surface area with mesoporous structures and stability of the CNTs and the high electrocatalytic activity of the metal sulfides. Overall, the designed composite CNT/metal-sulfide electrodes offer an important guideline for the development of next level energy conversion and energy storage devices.

Enhanced electrochemical capacitance of polyimidazole coated covellite CuS dispersed CNT composite materials for application in supercapacitors.

Great attention has been paid to the design and synthesis of distinct core/shell heterostructures for high-performance supercapacitors. We have prepared unique heterostructures consisting of polyimidazole-coated copper sulphide over a carbon nanotube network (CuS@CNT) on nickel foam, which was accomplished through a facile and cost-effective solvothermal method combined with a dip coating process. Hexagonal covellite CuS nanoparticles were dispersed on CNTs using a solvothermal method where dimethylformamide and distilled water were used as solvents. The synthesized CuS and CuS@CNT supercapacitor electrode materials were thoroughly characterized. The polymer supported electrode (PIM/CuS@CNT) shows a high areal capacitance of 1.51 F cm(-2) at a current density of 1.2 A g(-1), which is higher than the CuS@CNT electrode and many other previously reported CuS electrode materials. After 1000 cycles at a high current density of 1.2 A g(-1), the retention rate is 92%, indicating good long-term cycling stability. These results indicate that the PIM/CuS@CNT electrode is promising for high-performance supercapacitor applications.