Construction of Porous Aromatic Frameworks with Specifically Designed Motifs for Charge Storage and Transport.

ConspectusPorous frameworks possess high porosity and adjustable functions. The two features conjointly create sufficient interfaces for matter exchange and energy transfer within the skeletons. For crystalline porous frameworks, including metal organic frameworks (MOFs) and covalent organic frameworks (COFs), their long-range ordered structures indeed play an important role in managing versatile physicochemical behaviors such as electron transfer or band gap engineering. It is now feasible to predict their functions based on the unveiled structures and structure-performance relationships. In contrast, porous organic frameworks (POFs) represent a member of the porous solid family with no long-range regularity. For the case of POFs, the randomly packed building units and their disordered connections hinder the electronic structural consistency throughout the entire networks. However, many investigations have demonstrated that the functions of POFs could also be designed and originated from their local motifs.In this Account, we will first provide an overview of the design and synthesis principles for porous aromatic frameworks (PAFs), which are a typical family of POFs with high porosity and exceptional stability. Specifically, the functions achieved by the specific design and synthesis of in-framework motifs will be demonstrated. This strategy is particularly intuitive to introduce desired functions to PAFs, owing to the exceptional tolerance of PAFs to harsh chemical treatments and synthetic conditions. The local structures can be either obtained by selecting suitable building units, sometimes with the aid of computational screening, or emerge as the product of coupling reactions during the synthetic process. Radical PAFs can be obtained by incorporating a persistent radical molecule as a building unit, and the rigid and porous framework may facilitate the formation of radical species by trapping spins in the organic network, which could avoid the delocalizing and recombining processes. Alternatively, radical motifs can also be formed during the formation of the framework linkages. The coupling reaction plays an important role in the construction of functional motifs like diacetylene. The highly porous, radical PAFs showed significant performance as anodes of lithium-ion batteries. To improve the charge transport within the framework, the building units and their connecting manner were cohesively considered, and the framework with a fully conjugated backbone was built up. In another case, the explicit product of the cross-coupling reaction ensured the precise assembly of two building units with electron donating and accepting abilities; therefore, the moving direction of photogenerated electrons was rationally controlled. Constructing a fully conjugated backbone or rationally designing a D-A system for charge transfer in porous frameworks introduced exciting properties for photovoltaic and photocatalysis, and their highly porous, stable frameworks improved their functional applications for perovskite solar cells and chemical productions. These investigations shed light on the designable combination of intrinsic functional motifs with highly porous organic frameworks for effective energy storage and conversion.

Constructing Isoreticular Metal-Organic Frameworks by Silver-Carbon Bonds.

The incorporation of new coordinate bonds and the development of universal methods for new structures have always been of major interest in metal-organic framework (MOF) research. The poor reversibility makes metal-carbon (M-C) bonds a great challenge to adopt as linkages to construct crystalline MOFs. Herein, three isoreticular microcrystalline MOFs connected by silver-carbon (Ag-C) bonds are presented for the first time and named AgC-MOFs. Their structures contain a double coordination mode (σ and π) between Ag(I) and alkynyl. The three AgC-MOFs all exhibit three-dimensional (3D) frameworks with uniform one-dimensional (1D) hexagonal channels, and the pore width could be tuned from 1.1 to 1.8 nm. The construction of crystalline MOFs using poorly reversible Ag-C coordinate bonds extends the nexuses for the MOF structure and lights up more possibilities for the systematic design of MOFs.

Photocatalytic Extraction of Uranium from Seawater Using Covalent Organic Framework Nanowires.

In the push to achieve net-zero emissions by 2050, nuclear power will play an essential role alongside renewable wind and solar power, and correspondingly global interest and investment in this well-established technology is accelerating. The uranium present in seawater could support nuclear power generation for centuries, but traditional adsorptive separation strategies have proven ineffective for the selective extraction of uranium from this vast resource. Here, we report the synthesis of nanowires of a triazine-linked two-dimensional covalent organic framework via a solvent modulation approach, which can be used to access nanowire external diameters ranging from 50 to 200 nm. The 100 nm nanowires are exceptionally promising for the capture of uranium(VI) via photocatalytic reduction. Under simulated sunlight and without the use of sacrificial agents, the nanowires achieve a uranium uptake of 10.9 g/g from a 100 ppm uranyl(VI) solution, which is the highest reported to date among materials studied for photo and electrocatalytic uranium capture. Significantly, these nanowires exhibit a uranium adsorption capacity of 34.5 mg/g after exposure to seawater under irradiation for 42 days, a record among all materials reported to date for uranium capture.

Constructing Heterogeneous Interface by Growth of Carbon Nanotubes on the Surface of MoB2 for Boosting Hydrogen Evolution Reaction in a Wide pH Range.

Transition metal diborides represented by MoB2 have attracted widespread attention for their excellent acidic hydrogen evolution reaction (HER). Nevertheless, their electrocatalytic performance is generally unsatisfactory in high-pH electrolytes. Heterogeneous interface engineering is one of the most promising methods for optimizing the composition and structure of electrocatalysts, thereby greatly affecting their electrochemical performance. Herein, a heterostructure, composed of MoB2 and carbon nanotubes (CNTs), is rationally constructed by boronizing precursors including (NH4 )4 [NiH6 Mo6 O24 ]·5H2 O (NiMo6 ) and Co complexes on the carbon cloth (Co,Ni-MoB2 @CNT/CC). In this method, NiMo6 is boronized to form MoB2 by a modified molten-salt-assisted borothermal reduction. Meanwhile, Co catalyzes extra carbon sources to grow CNTs on the surface of MoB2 . Thanks to the successful production of the heterostructure, Co,Ni-MoB2 @CNT/CC exhibits remarkable HER performance with a low overpotential of 98.6, 113.0, and 73.9 mV at 10 mA cm-2 in acidic, neutral, and alkaline electrolytes, respectively. Notably, even at 500 mA cm-2 , the electrochemical activity of Co,Ni-MoB2 @CNT/CC exceeds that of Pt/C/CC in an alkaline solution and maintains over 50 h. Theoretical calculations reveal that the construction of the heterostructure is beneficial to both water dissociation and reactive intermediate adsorption, resulting in superior alkaline HER performance.

Residue-Free Orally Administered Drug Carrier Based on a Porous Aromatic Framework for Efficient Multisite Treatment.

Nowadays, oral medications are the primary method of treating disease due to their convenience, low cost, and safety, without the need for complex medical procedures. To maximize treatment effectiveness, almost all oral medications utilize drug carriers, such as capsules, liposomes, and sugar coatings. However, these carriers rely on dissolution or fragmentation to achieve drug release, which leads to drugs and carriers coabsorption in the body, causing unnecessary adverse drug reactions, such as nausea, vomiting, abdominal pain, and even death caused by allergy. Therefore, the ideal oral drug carrier should avoid degradation and absorption and be totally excreted after drug release at the desired location. Herein, a gastrointestinally stable oral drug carrier based on porous aromatic framework-1 (PAF-1) is constructed, and it is modified with famotidine (a well-known gastric drug) and mesalazine (a well-known ulcerative colitis drug) to verify the excellent potential of PAF-1. The results demonstrate that PAF-1 can accurately release famotidine in stomach, mesalazine in the intestine, and finally be completely excreted from the body without any residue after 12 h. The use of PAF materials for the construction of oral drug carriers with no residue in the gastrointestinal tract provides a new approach for efficient disease treatment.

Continuous Ultrathin Zwitterionic Covalent Organic Framework Membrane Via Surface-Initiated Polymerization Toward Superior Water Retention.

Efficient construction of proton transport channels in proton exchange membranes maintaining conductivity under varied humidity is critical for the development of fuel cells. Covalent organic frameworks (COFs) hold great potential in providing precise and fast ion transport channels. However, the preparation of continuous free-standing COF membranes retaining their inherent structural advantages to realize excellent proton conduction performance is a major challenge. Herein, a zwitterionic COF material bearing positive ammonium ions and negative sulphonic acid ions is developed. Free-standing COF membrane with adjustable thickness is constructed via surface-initiated polymerization of COF monomers. The porosity, continuity, and stability of the membranes are demonstrated via the transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) characterization. The rigidity of the COF structure avoids swelling in aqueous solution, which improves the chemical stability of the proton exchange membranes and improves the performance stability. In the higher humidity range (50-90%), the prepared zwitterionic COF membrane exhibits superior capability in retaining the conductivity compared to COF membrane merely bearing sulphonic acid group. The established strategy shows the potential for the application of zwitterionic COF in the proton exchange membrane fuel cells.

Ionic Porous Aromatic Frameworks Embedding Polyoxometalates for Heterogeneous Catalysis.

Porous aromatic frameworks (PAFs) are highly promising functional porous solids known for their feasible amenability and extraordinary stability. When the framework was modified by ionic functional groups, these ionic PAFs (iPAFs) exhibited charged channels for adsorption, separation, and catalysis. However, the surface areas of ionic porous frameworks are usually lower than that of neutral frameworks, and their synthesis is limited by specific strategies and complex modification processes. To address these challenges, an intuitive route to construct ionic porous framework with high specific surface area was proposed. Herein, a multivariate ionic porous aromatic framework (MTV-iPAFs, named PAF-270) was synthesized using readily available building units with ionic functional groups through a multivariable synthesis strategy. PAF-270 exhibited hierarchical structure with the highest specific surface area among reported imidazolium-functionalized PAFs. Utilizing its physical and chemical properties, the availability for polyoxometalate loading and heterogeneous catalysis of PAF-270 were explored. PAF-270 exhibited a high adsorption capacity up to 50 % for both H3O40PW12 (HPW) and (NH4)5H6PV8Mo4O40 (V8). HPW@PAF-270 and V8@PAF-270 exhibited excellent catalytic abilities for oleic acid esterification and extractive oxidative desulfurization, respectively. Due to the stability of PAFs, these materials also showed remarkable resistance to temperature and pH changes. Overall, these results underscore the potential application of MTV-iPAFs as versatile functional porous materials.

Confinement Synthesis of Atomic Copper-Anchored Polymeric Carbon Nitride in Crystalline UiO-66-NH2 for High-Performance CO2-to-CH3OH Photocatalysis.

Photocatalytic CO2 reduction to value-added fuels displays an attractive scenario to enhance energy supply and reduce global warming. We report herein the confinement synthesis of polymeric carbon nitride (PCN) incorporating with Cu single atoms (CuSAs) inside the crystalline UiO-66-NH2, which combines the merits of heterojunction photocatalysis and single-atom catalysis (SAC) to achieve high-performance CO2-to-CH3OH conversion. A series of spectral studies displays the formation of CuSAs@PCN inside the crystalline UiO-66-NH2. Remarkably, the ternary composite shows an excellent photocatalytic turnover frequency of 4.15 mmol·h-1·g-1 for CO2-to-CH3OH conversion. Theoretical and experimental studies demonstrate the doping of CuSAs, as well as the formation of type-II heterojunction, are causal factors to achieve CH3OH generation. The study provides new insights designing high-performance photocatalyst for CO2 conversion to fuels at atomic scale.

Rationally Designed Cyclooctatetrathiophene-Based Porous Aromatic Frameworks (COTh-PAFs) for Efficient Photocatalytic Hydrogen Peroxide Production.

Constructing stable and efficient photocatalysts for H2O2 production is of great importance and is challenging. In this study, the synthesis of three photoactive cyclooctatetrathiophene (COTh)-based porous aromatic frameworks (COTh-PAFs) in an alternating donor-acceptor (D-A) fashion is presented. In combination with a triazine-derived electron acceptor, PAF-363 exhibits high efficiency for the photosynthesis of H2O2 with production rates of 11733 µmol g-1 h-1(with sacrificial agent) and 3930 µmol g-1 h-1 (without sacrificial agent) from water and oxygen under visible light irradiation. Experimental results and theoretical calculations reveal that the charge transfer positions and the O2 adsorption sites in PAF-363 are both concentrated on COTh fragments, which facilitate the H2O2 production through the oxygen reduction reaction (ORR) pathway. This work highlights that the rational design of COTh-PAFs with consideration of D-A direction, charge transfer positions, and O2 adsorption sites provides a feasible access to efficient H2O2 production photocatalysts.

Boosting H+ Storage in Aqueous Zinc Ion Batteries via Integrating Redox-Active Sites into Hydrogen-Bonded Organic Frameworks with Strong π-π Stacking.

In the emerging aqueous zinc ion batteries (AZIBs), proton (H+ ) with the smallest molar mass and fast (de)coordination kinetics is considered as the most ideal charge carrier compared with Zn2+ counterpart, however, searching for new hosting materials for H+ storage is still at its infancy. Herein, redox-active hydrogen-bonded organic frameworks (HOFs) assembled from diaminotriazine moiety decorated hexaazatrinnphthalene (HOF-HATN) are for the first time developed as the stable cathode hosting material for boosting H+ storage in AZIBs. The unique integration of hydrogen-bonding networks and strong π-π stacking endow it rapid Grotthuss proton conduction, stable supramolecular structure and inclined H+ storage. As a consequence, HOF-HATN displays a high capacity (320 mAh g-1 at 0.05 A g-1 ) and robust cyclability of (>10000 cycles at 5 A g-1 ) based on three-step cation coordination storage. These findings get insight into the proton transport and storage behavior in HOFs and provide the molecular engineering strategy for constructing well-defined cathode hosting materials for rechargeable aqueous batteries.