Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2.

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO2 from gas mixtures via O─C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13C-labeled CO2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol-1 between CO2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO2 insertion. The as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO2 in crystalline scaffolds.

Tailoring the Coordination Micro-Environment in Nanotraps for Efficient Platinum/Palladium Separation.

Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high-tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties. Herein, a breakthrough approach is presented by sophisticatedly tailoring the coordination micro-environment in a series of aminopyridine-based porous organic polymers, which enables the creation of platinum-specific nanotraps for efficient separation of binary PGMs (platinum/palladium). The newly synthesized POP-o2NH2-Py demonstrates record uptakes and selectivity toward platinum over palladium, with the amino groups adjacent to the pyridine moieties being vital in improving platinum binding performance. Further breakthrough experiments underline its remarkable ability to separate platinum and palladium. Spectroscopic analysis reveals that POP-o2NH2-Py offers a more favorable coordination fashion to platinum ions compared to palladium ions owing to the greater interaction between N and Pt4+ and stronger intramolecular hydrogen bonding between the amino groups and four coordinating chlorines at platinum. These findings underscore the importance of fine-tuning the coordination micro-environment of nanotraps through subtle modifications that can greatly enhance the selectivity toward the desired metal ions.

Porous Materials for Water Purification.

Water pollution is a growing threat to humanity due to the pervasiveness of contaminants in water bodies. Significant efforts have been made to separate these hazardous components to purify polluted water through various methods. However, conventional remediation methods suffer from limitations such as low uptake capacity or selectivity, and current water quality standards cannot be met. Recently, advanced porous materials (APMs) have shown promise in improved segregation of contaminants compared to traditional porous materials in uptake capacity and selectivity. These materials feature merits of high surface area and versatile functionality, rendering them ideal platforms for the design of novel adsorbents. This Review summarizes the development and employment of APMs in a variety of water treatments accompanied by assessments of task-specific adsorption performance. Finally, we discuss our perspectives on future opportunities for APMs in water purification.

Uranium extraction from seawater: material design, emerging technologies and marine engineering.

Uranium extraction from seawater (UES), a potential approach to securing the long-term uranium supply and sustainability of nuclear energy, has experienced significant progress in the past decade. Promising adsorbents with record-high capacities have been developed by diverse innovative synthetic strategies, and scale-up marine field tests have been put forward by several countries. However, significant challenges remain in terms of the adsorbents' properties in complex marine environments, deployment methods, and the economic viability of current UES systems. This review presents an up-to-date overview of the latest advancements in the UES field, highlighting new insights into the mechanistic basis of UES and the methodologies towards the function-oriented development of uranium adsorbents with high adsorption capacity, selectivity, biofouling resistance, and durability. A distinctive emphasis is placed on emerging electrochemical and photochemical strategies that have been employed to develop efficient UES systems. The most recent achievements in marine tests by the major countries are summarized. Challenges and perspectives related to the fundamental, technical, and engineering aspects of UES are discussed. This review is envisaged to inspire innovative ideas and bring technical solutions towards the development of technically and economically viable UES systems.

Nanospace Decoration with Uranyl-Specific "Hooks" for Selective Uranium Extraction from Seawater with Ultrahigh Enrichment Index.

Mining uranium from seawater is highly desirable for sustaining the increasing demand for nuclear fuel; however, access to this unparalleled reserve has been limited by competitive adsorption of a wide variety of concentrated competitors, especially vanadium. Herein, we report the creation of a series of uranyl-specific "hooks" and the decoration of them into the nanospace of porous organic polymers to afford uranium nanotraps for seawater uranium extraction. Manipulating the relative distances and angles of amidoxime moieties in the ligands enabled the creation of uranyl-specific "hooks" that feature ultrahigh affinity and selective sequestration of uranium with a distribution coefficient threefold higher compared to that of vanadium, overcoming the long-term challenge of the competing adsorption of vanadium for uranium extraction from seawater. The optimized uranium nanotrap (2.5 mg) can extract more than one-third of the uranium in seawater (5 gallons), affording an enrichment index of 3836 and thus presenting a new benchmark for uranium adsorbent. Moreover, with improved selectivity, the uranium nanotraps could be regenerated using a mild base treatment. The synergistic combination of experimental and theoretical analyses in this study provides a mechanistic approach for optimizing the selectivity of chelators toward analytes of interest.

N-Dimethylation and N-Functionalization of Amines Using Ru Nanoparticle Catalysts and Formaldehyde or Functional Aldehydes as the Carbon Source.

N-methylated amines are essential bioactive compounds and have been widely used in the fine and bulk chemical industries, as well as in pharmaceuticals, agrochemicals, and dyes. Developing green, efficient, and low-cost catalysts for methylation of amines by using efficient and easily accessible methylating reagents is highly desired yet remains a significant challenge. Herein, we report the selective N-dimethylation of different functional amines with different functional aldehydes under easy-to-handle and industrially applicable conditions using carbon-supported Ru nanoparticles (Ru/C) as a heterogeneous catalyst. A broad spectrum of amines could be efficiently converted to their corresponding N,N-dimethyl amines with good compatibility of various functional groups. This method is widely applicable to N-dimethylation of primary amines including aromatic, aliphatic amines with formaldehyde, and synthesis of tertiary amines from primary, secondary amines with different functional aldehydes. The advantage of this newly described method includes operational simplicity, high turnover number, the ready availability of the catalyst, and good functional group compatibility. This Ru/C catalyzed N-dimethylation reaction possibly proceeds through a two-step N-methylation reaction process.

Earth-abundant Metal-catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis.

Nitrogen-containing compounds, as an important class of chemicals, have been used widely in pharmaceuticals, materials synthesis. Transition metal-catalyzed reductive amination of an aldehyde or a ketone with ammonia or an amine has been proved to be an efficient and practical method for the preparation of nitrogen-containing compounds in academia and industry for a century. Given the above, several effective methods using transition metals have been developed in recent years. Noble transition metals like Pd, Pt, and Au-based catalysts have been predominately used in reductive amination. Because of their high prices, strict official regulations of residues in pharmaceuticals, and deleterious effects on the biological system, their industrial applications are severely hampered. With the increasing sustainable and environmental problems, the Earth-abundant transition metals including Ti, Fe, Co, Ni, and Zr have also been investigated for the reductive amination reaction and showed great potential to the advancement of sustainable and cost-effective reductive amination processes. This critical review will mainly summarize the work using Earth-abundant metals. The effects of different transition metals used in catalytic reduction amination were discussed and compared, and some suggestions were given. The last section highlights the catalytic activities of bi- and tri-metallic catalysts. Indeed, this latter family is very promising and simultaneously benefits from increased stability, and selectivity, compared to monometallic NPs, due to synergistic substrate activation. Few comprehensive reviews focusing on Earth-abundant transition metals catalyst has been published since 1948, although several authors reported some summaries dealing with one or the other part of this aspect. It is hoped that this critical review will inspire researchers to develop new efficient and selective earth-abundant metal catalysts for highly, environmentally sustainable reductive amination methods, as well as improve the pharmaceutical industry and related chemical synthesis company traditional method with the utilization of the green method widely.

Highly Stable Single Crystals of Three-Dimensional Porous Oligomer Frameworks Synthesized under Kinetic Conditions.

Various robust, crystalline, and porous organic frameworks based on in situ-formed imine-linked oligomers were investigated. These oligomers self-assembled through collaborative intermolecular hydrogen bonding interactions via liquid-liquid interfacial reactions. The soluble oligomers were kinetic products with multiple unreacted aldehyde groups that acted as hydrogen bond donors and acceptors and directed the assembly of the resulting oligomers into 3D frameworks. The sequential formation of robust covalent linkages and highly reversible hydrogen bonds enforced long-range symmetry and facilitated the production of large single crystals, with structures that were unambiguously determined by single-crystal X-ray diffraction. The unique hierarchical arrangements increased the steric hindrance of the imine bond, which prevented attacks from water molecules, greatly improving the stability. The multiple binding sites in the frameworks enabled rapid sequestration of micropollutant in water.

Spatial Engineering Direct Cooperativity between Binding Sites for Uranium Sequestration.

Preorganization is a basic design principle used by nature that allows for synergistic pathways to be expressed. Herein, a full account of the conceptual and experimental development from randomly distributed functionalities to a convergent arrangement that facilitates cooperative binding is given, thus conferring exceptional affinity toward the analyte of interest. The resulting material with chelating groups populated adjacently in a spatially locked manner displays up to two orders of magnitude improvement compared to a random and isolated manner using uranium sequestration as a model application. This adsorbent shows exceptional extraction efficiencies, capable of reducing the uranium concentration from 5 ppm to less than 1 ppb within 10 min, even though the system is permeated with high concentrations of competing ions. The efficiency is further supported by its ability to extract uranium from seawater with an uptake capability of 5.01 mg g-1, placing it among the highest-capacity seawater uranium extraction materials described to date. The concept presented here uncovers a new paradigm in the design of efficient sorbent materials by manipulating the spatial distribution to amplify the cooperation of functions.

Rational design of bifunctional conjugated microporous polymers.

Conjugated microporous polymers (CMPs) are an emerging class of porous organic polymers that combine π-conjugated skeletons with permanent micropores. Since their first report in 2007, the enormous exploration of linkage types, building units, and synthetic methods for CMPs have facilitated their potential applications in various areas, from gas separations to energy storage. Owning to their unique construction, CMPs offer the opportunity for the precise design of conjugated skeletons and pore environment engineering, which allow the construction of functional porous materials at the molecular level. The capability to chemically alter CMPs to targeted applications allows for the fine adaptation of functionalities for the ever-changing environments and necessities. Bifunctional CMPs are a branch of functionalized CMPs that have caught the interest of researchers because of their inherent synergistic systems that can expand their applications and optimize their performance. This review discusses the rational design and synthesis of bifunctional CMPs and summarizes their advanced applications. To conclude, our own perspective on the research prospects of these types of materials is outlined.

Secondary Sphere Effects on Porous Polymeric Organocatalysts for CO2 Transformations: Subtle Modifications Resulting in Superior Performance.

Albeit harnessing secondary sphere interactions to exert control over the reaction outcomes has primarily been applied to enzymatic and organometallic catalysis, there are seldom any studies that introduce outer-sphere modifiers into organocatalysts. This is even less in the corresponding heterogeneous catalytic system. In this contribution, we experimentally and computationally investigate the role of secondary effects in the reactivity of bromide anions toward CO2 transformations. Six pyridinium cationic porous frameworks have been synthesized and fully characterized. Structure-activity relationships and kinetics show that the type and the location of the substituents on the cationic framework have a significant impact on the nucleophilic reactivity of their bromide counter anion. Specifically, the attachment of amine substituent to the ortho position relative to a pyridinium motif produces a remarkably efficient catalyst for CO2 transformation, by a factor of six times greater in comparison to the pristine pyridinium-based polymer. The hydrogen-bond-interaction-promoted reagent activation and enhanced delocalization ability of bromide counter anion are believed to be the key to driving the reaction toward CO2 utilization. These observations, therefore, champion the leverage of secondary interaction for optimizing the reactivity of organocatalysts.

Tailored Porous Organic Polymers for Task-Specific Water Purification.

The Industrial Revolution has resulted in social and economic improvements, but unfortunately, with the development of manufacturing and mining, water sources have been pervaded with contaminants, putting Earth's freshwater supply in peril. Therefore, the segregation of pollutants-such as radionuclides, heavy metals, and oil spills-from water streams, has become a pertinent problem. Attempts have been made to extract these pollutants through chemical precipitation, sorbents, and membranes. The limitations of the current remediation methods, including the generation of a considerable volume of chemical sludge as well as low uptake capacity and/or selectivity, actuate the need for materials innovation. These insufficiencies have provoked our interest in the exploration of porous organic polymers (POPs) for water treatment. This category of porous material has been at the forefront of materials research due to its modular nature, i.e., its tunable functionality and tailorable porosity. Compared to other materials, the practicality of POPs comes from their purely organic composition, which lends to their stability and ease of synthesis. The potential of using POPs as a design platform for solid extractors is closely associated with the ease with which their pore space can be functionalized with high densities of strong adsorption sites, resulting in a material that retains its robustness while providing specified interactions depending on the contaminant of choice.POPs raise opportunities to improve current or enable new technologies to achieve safer water. In this Account, we describe some of our efforts toward the exploitation of the unique properties of POPs for improving water purification by answering key questions and proposing research opportunities. The design strategies and principles involved for functionalizing POPs include the following: increasing the density and flexibility of the chelator to enhance their cooperation, introducing the secondary sphere modifiers to reinforce the primary binding, and enforcing the orientation of the ligands in the pore channel to increase the accessibility and cooperation of the functionalities. For each strategy, we first describe its chemical basis, followed by presenting examples that convey the underlying concepts, giving rise to functional materials that are beyond the traditional ones, as demonstrated by radionuclide sequestration, heavy metal decontamination, and oil-spill cleanup. Our endeavors to explore the applicability of POPs to deal with these high-priority contaminants are expected to impact personal consumer water purifiers, industrial wastewater management systems, and nuclear waste management. In our view, more exciting will be new applications and new examples of the functionalization strategies made by creatively merging the strategies mentioned above, enabling increasingly selective binding and efficiency and ultimately promoting POPs for practical applications to enhance water security.

Opportunities of Covalent Organic Frameworks for Advanced Applications.

Covalent organic frameworks (COFs) are an emerging class of functional nanostructures with intriguing properties, due to their unprecedented combination of high crystallinity, tunable pore size, large surface area, and unique molecular architecture. The range of properties characterized in COFs has rapidly expanded to include those of interest for numerous applications ranging from energy to environment. Here, a background overview is provided, consisting of a brief introduction of porous materials and the design feature of COFs. Then, recent advancements of COFs as a designer platform for a plethora of applications are emphasized together with discussions about the strategies and principles involved. Finally, challenges remaining for this type material for real applications are outlined.

Conversion of industrial biowastes to clean solid fuels via hydrothermal carbonization (HTC): Upgrading mechanism in relation to coalification process and combustion behavior.

The aim of this work was to study the correlation between dynamic mechanisms of carbon structure associated with their upgrading effects with the help of XPS, 13C NMR and 2D-PCIS methods. Results showed the fuel qualifies of biowastes were improved and became comparable to lignite or even bitumite after HTC. The carbon chemical bonds of -C-H and -C-O in biowaste components (mainly protein and polysaccharide) were thermally cracked and enriched in liquid phase in the form of soluble intermediates, which subsequently generated coal-like structures via cyclization as well as polymerization at higher temperatures. The further investigation on thermogravimetric analysis found that the conversion of "-C-H/C-O to aromatic -C-C/CC" was beneficial for stabilizing their combustion behavior by integrating two stages of biowastes (devolatilization stage and combustion stage) into one stage of hydrochars (combustion stage).

Denitrification and desulphurization of industrial biowastes via hydrothermal modification.

In attempt to decrease NOX and SO2 emission from thermochemical utilization, three industrial biowastes (penicillin mycelia waste, sewage sludge and peat waste) contained high nitrogen (N) and sulfur (S) were chosen to investigate the denitrification and desulphurization of hydrothermal modification. The results demonstrated that hydrothermal modification destroyed the structure of N- and S-containing components, thereby altering their existed conformations. Inorganic-N (N-IN) and most of amino-N/polyamide-N (N-A) were enriched by liquid phase in the forms of NH4+-N and soluble organic-N (Org-N), respectively; subsequently, Org-N could further decompose to NH4+-N at higher temperature. Residual N in hydrochars was converted from N-A to heterocyclic-N (pyrrolic-N, pyridinic-N and quaternary-N) via hydrolysis and cyclization. Similarly, over 60% of S was remove form biowastes at 240 °C. In solid phase, part of organic-S was altered to thiophenes-S after modified, while the remainder was transformed to inorganic-S; but the variation of inorganic-S in hydrochars strongly affected by its specific species.

The transformation pathways of nitrogen in sewage sludge during hydrothermal treatment.

Hydrothermal treatment (HT) has been proved as a significant pretreatment in decreasing emissions of NOX pollutants from thermochemical utilization of sewage sludge (SS) derived solid fuel. This study aims to investigate the denitrification of HT and the redistribution of nitrogen (N) in different products so as to speculate the comprehensive pathway of N transformation during hydrothermal process. Results found that only 20% of N remained in hydrochar, whereas the rest of N (nearly 80%) was transformed into other phase. A majority of amino-N in SS was enriched in liquid phase in the form of Org-N at first, then further decomposed to NH4+-N. The remaining amino-N converted to pyrrole-N, pyridine-N and quaternary-N as temperature progresses. Meanwhile, amine-N derived from protein-N formed heterocyclic-N in oil phase via Diels-Alder reaction. NH3, the major nitrogenous gas, was dissolved in liquid as NH4+-N immediately after producing, but increased with prolonged reaction time.