Pd "Kills Two Birds with One Stone" for the Synthesis of Catalyst: Dual Active Sites of Pd Triggers the Kinetics of O2 Electrocatalysis.

Noble metal-based catalyst, despite their exorbitant cost, are the only successful catalyst for bifunctional oxygen electrocatalysis owing to their capability to drive forward the reaction rate kinetically. Therefore, it is desirable to diminish the noble metal loading without any compromise in the catalyst performance. In this study, the aim to achieve two goals with one action via a single-step route to have ultra-low loading of Pd in the catalyst. The Pd is used as a catalyst for C─C bond formation followed by complexation reactions or vice versa, in conventional Suzuki-Miyaura cross-coupling (SMCC) reaction, which yields a Pd-based porous organic polymer. Interestingly, it is found that dispersed Pd nanocluster (PdNC ) is present together with Pd single atom doped into nanocarbon (Pd-NC) matrix in the catalyst (PdNC /Pd-NC800 ) that obtained after pyrolysis of the porous polymer. The catalyst exhibits remarkable bifunctional activity and durability towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Further, it is studied that the in situ attenuated total reflection infrared (ATR-IR) spectroscopy at different electrochemical potentials during ORR and OER to observe the reaction intermediates. The homemade zinc-air battery with the catalyst displayed great performance, establishing the significance of PdNC /Pd-NC800 as a bifunctional oxygen electrocatalyst.

Enhanced Activity of Small Pt Nanoparticles Decorated with High-Loading Single Fe─N4 for Methanol Oxidation and Oxygen Reduction via the Assistive Active Sites Strategy.

Decorating platinum (Pt) with a single atom offers a promising approach to tailoring their catalytic activity. In this study, for the first time, an innovative assistive active sites (AAS) strategy is proposed to construct high-loading (3.46wt.%) single Fe─N4 as AAS, which are further hybridized with small Pt nanoparticles to enhance both oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activities. For ORR, the target catalyst (Pt/HFeSA-HCS) exhibits a higher mass activity (MA) of 0.98 A mgPt -1 and specific activity (SA) of 1.39 mA cmPt -2 at 0.90 V versus RHE. As for MOR, Pt/HFeSA-HCS shows exceptional MA (3.21 A mgPt -1) and SA (4.27 mA cmPt -2) at peak values, surpassing commercial Pt/C by 15.3 and 11.5 times, respectively. The underlying mechanism behind this AAS strategy is to find that in MOR, Fe─N4 promotes water dissociation, generating more *OH to accelerate the conversion of *CO to CO2. Meanwhile, in ORR, Fe─N4 acts as a competitor to adsorb *OH, weakening Pt─OH bonding and facilitating desorption of *OH on the Pt surface. Constructing AAS that can enhance dual functionality simultaneously can be seen as a successful "kill two birds with one stone" strategy.

Electrochemical Formation of Ionic Porous Organic Polymers Based on Viologen for Electrochromic Applications.

The systematic study of two ionic porous organic polymers (iPOPs) based on viologens and their first applications in the electrochromic field are reported. The viologen-based iPOPs are synthesized by electrochemical polymerization with cyano groups, providing a simple and controllable method for iPOPs that solves the film preparation problems common to viologens. After the characterization of these iPOPs, a detailed study of their electrochromic properties is conducted. The iPOP films based on viologens structure exhibit excellent electrochromic properties. In addition, the resulting iPOP films show high sensitivity to electrolyte ions of different sizes in the redox process. Electrochemical and electrochromic data of the iPOPs explain this phenomenon in detail. These results demonstrate that iPOPs of this type are ideal candidates as electrochromic materials due to their inherent porous structures and ion-rich properties.

Green synthesis of magnetic azo-linked porous organic polymers with recyclable properties for enhanced Bisphenol-A adsorption from aqueous solutions.

Porous organic polymers (POPs) present superior adsorption performance to steroid endocrine disruptors. However, the effective recovery and high cost have been a big limitation for their large-scale applications. Herein, magnetic azo-linked porous polymers (Fe3O4@SiO2/ALP-p) were designed and prepared in a green synthesis approach using low-price materials from phloroglucinol and pararosaniline via a diazo-coupling reaction under standard temperature and pressure conditions, which embedded with Fe3O4@SiO2 nanoparticles to form three-dimensional interlayer network structure with flexible-rigid interweaving. The saturated adsorption capacity to bisphenol-A (BPA) was 485.09 mg/g at 298 K, which increased by 1.4 times compared with ALP-p of relatively smaller mass density. This enhanced adsorption was ascribed to increment from surface adsorption and pore filling with 2.3 times of specific surface area and 2.6 times of pore volume, although the total organic functional groups decreased with Fe3O4@SiO2 amendment. Also, the adsorption rate increased by about 1.1 and 1.5-fold due to enhancement in the initial stage of surface adsorption and subsequent stage pore diffusion, respectively. Moreover, this adsorbent could be used in broad pH (3.0-7.0) and salinity adaptability (<0.5 mol/L). The loss of adsorption capacity and magnetic recovery were lower than 1.1% and 0.8% in each operation cycle because of the flexible-rigid interweave. This excellent performance was contributed by synergistic effects from physisorption and chemisorption, such as pore filling, electrostatic attraction, π-π stacking, hydrogen bonding, and hydrophobic interaction. This study offered a cost-effective, high-performing, and ecologically friendly material along with a green preparation method.

Integrating porphyrin-based nanoporous organic polymers with electrochemical aptasensors for ultratrace detection of kanamycin.

The synthesis and characterization of two new porphyrin-based porous organic polymers (POPs) via Sonogashira cross-coupling reaction and leverage the two obtained POPs is reported for the fabrication of electrochemical aptasensors to detect kanamycin at an ultratrace level. The resultant electrochemical aptasensor demonstrates a high linear relationship with the logarithmic value of kanamycin concentration in the range 5 × 10-5-5 µg/L with the limit of detection of 17.6 pg/L or 36.3 fM. During the analysis of real samples from milk and river, a relative standard deviation of less than 4.39%, and good recovery values in the range 97.0-105% were obtained.

Metal-Free Activation of Molecular Oxygen by 9-Fluorenone-Based Porous Organic Polymers for Selective Aerobic Oxidation.

Oxygen activation is a critical step in heterogeneous oxidative processes, particularly in catalytic, electrolytic, and pharmaceutical applications. Among the various catalysts available for photocatalytic O2 activation, homogeneous aryl ketones are at the forefront. To avoid the degradation and deactivation of aryl ketones, 9-fluorenone-based porous organic polymers were designed and regulated by doping them with co-monomers. The obtained heterogeneous photocatalyst showed good performance in O2 activation, and its performance was better than that of homogeneous 9-fluorenone. The obtained heterogeneous photocatalyst showed good reusability. We believe that the presented method and findings represent an important step toward designing catalysts tailored for specific tasks.

Engineering Single-Atom Sites with the Irving-Williams Series for the Simultaneous Co-photocatalytic CO2 Reduction and CH3CHO Oxidation.

The bonding effects between 3d transition-metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition-metal atoms of the spontaneous geometrical distortions, that is the Jahn-Teller effect, can alter CFSE, thereby leading to the Irving-Williams series. However, engineering single-atom sites (SASs) using the Irving-Williams series as an ideal guideline has not been reported to date. Herein, alkynyl-linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving-Williams series was employed to accurately predict the bonding effects between 3d transition-metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu-SASs/CPFs exhibits higher stability and faster charge-transfer efficiency, far surpassing other metal-SASs/CPFs. As expected, Cu-SASs/CPFs demonstrates a high photoreduction of CO2-to-CO activity (~30.3 µmol ⋅ g-1 ⋅ h-1) and an exceptional photooxidation of CH3CHO-to-CH3COOH activity (~24.7 µmol ⋅ g-1 ⋅ h-1). Interestingly, the generated *O2 - is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving-Williams to regulate the catalytic performances.

Enhancing the Crystallinity of Keto-enamine-Linked Covalent Organic Frameworks through an in situ Protection-Deprotection Strategy.

ß-Keto-enamine-linked 2D covalent organic frameworks (COFs) have emerged as highly robust materials, showing significant potential for practical applications. However, the exclusive reliance on 1,3,5-triformylphloroglucinol (Tp aldehyde) in the design of such COFs often results in the production of non-porous amorphous polymers when combined with certain amine building blocks. Attempts to adjust the crystallinity and porosity by a modulator approach are inefficient because Tp aldehyde readily forms stable ß-keto-enamine-linked monomers/oligomers with various aromatic amines through an irreversible keto-enol tautomerization process. Our research employed a unique protection-deprotection strategy to enhance the crystallinity and porosity of ß-keto-enamine-linked squaramide-based 2D COFs. Advanced solid-state NMR studies, including 1D 13 C CPMAS, 1 H fast MAS, 15 N CPMAS, 2D 13 C-1 H correlation, 1 H-1 H DQ-SQ, and 14 N-1 H HMQC NMR were used to establish the atomic-level connectivity within the resultant COFs. The TpOMe -Sqm COFs synthesized utilizing this strategy have a surface area of 487 m2 g-1 , significantly higher than similar COFs synthesized using Tp aldehyde. Furthermore, detailed time-dependent PXRD, solid-state 13 C CPMAS NMR, and theoretical DFT studies shed more light on the crystallization and linkage conversion processes in these 2D COFs. Ultimately, we applied this protection-deprotection method to construct novel keto-enamine-linked highly porous organic polymers with a surface area of 1018 m2 g-1 .

Trapping Halogen Anions in Cationic Viologen Porous Organic Polymers for Highly Cycling-Stable Cathode Materials.

Halogens, especially Br2 and I2 , as cathode materials for lithium-ion batteries exhibit high energy density with low cost, but poor cycling performance due to their high solubility in electrolyte solution. Herein, viologen-based cationic porous organic polymers (TpVXs, X = Cl, Br, or I) with abundant pores and ionic redox-active moieties are designed to immobilize halogen anions stoichiometrically. TpVBr and TpVI electrodes exhibit high initial specific capacity (116 and 132 mAh g-1 at 0.2 C) and high average discharge voltage (≈3.0 V) without any host materials. Notably, benefiting from the porous and ionic structure, TpVBr and TpVI present excellent long-term cycling stability (86% and 98% capacity retention after 600 cycles at 0.5 C), which are far superior to those of the state-of-the-art halogen electrodes. In addition, the charge storage mechanism is investigated by in situ Raman and ex situ X-ray photoelectron spectroscopy.

Porous Supramolecular Assemblies for Efficient Suzuki Coupling of Aryl Chlorides.

The development of catalytic systems that can activate aryl chlorides for palladium-catalyzed cross-coupling reactions is at the forefront of ongoing efforts to synthesize fine chemicals. In this study, a facile ligand-template approach is adopted to achieve active-site encapsulation by forming supramolecular assemblies; this bestowed the pristine inert counterparts with reactivity, which is further increased upon the construction of a porous framework. Experimental results indicated that the isolation of ligands by the surrounding template units is key to the formation of catalytically active monoligated palladium complexes. Additionally, the construction of porous frameworks using the resulting supramolecular assemblies prevented the decomposition of the Pd complexes into nanoparticles, which drastically increased the catalyst lifetime. These findings, along with the simplicity and generality of the synthesis scheme, suggest that the strategy can be leveraged to achieve unique reactivity and potentially enable fine-chemical synthesis.

Two-Dimensional Covalent Organic Frameworks as Tailor-Made Scaffolds for Water Harvesting.

Developing materials to harvest water from the air is of great importance to alleviate the water shortage for people living in arid regions, where the annual average relative humidity (RH) is lower than 0.4. In this work, we report a general nitrogen atom incorporation strategy to prepare high-performance covalent organic frameworks (COFs) for water harvesting from the air in arid areas. A series of COFs, namely COF-W1, COF-W2, and COF-W3 were developed for this purpose. Different contents of nitrogen were embedded into COFs by incorporating pyridine units into the building blocks. With the increasing content of nitrogen from COF-W1 to COF-W3, the inflection points of their water isotherms shift distinctly from RH values from 0.65 to 0.25. Significantly, COF-W3 exhibits the lowest inflection point at a low RH value of 0.25 and reaches a high uptake capacity of 0.28 g g-1 at 25 °C with a low hysteresis loop. Moreover, the gram-scale COF-W3 retains its high performance, which renders it more attractive in water harvesting. This work demonstrates the feasibility of this nitrogen incorporation strategy to acquire high-performance COFs as water harvesters in the future.

Carbon-Carbon Linked Organic Frameworks: An Explicit Summary and Analysis.

Organic frameworks with carbon-carbon (CC) linkage are an important class of materials owing to their outstanding chemical stability and extended π-electron delocalization resulting in unique optoelectronic properties. In the first part of this review article, the design principles for the bottom-up synthesis of 2D and 3D sp/sp2 CC linked organic frameworks are summarized. Representative reaction methodologies, such as Knoevenagel condensation, Aldol condensation, Horner-Wadsworth-Emmons reaction, Wittig reaction, and coupling reactions (Ullmann, Suzuki, Heck, Yamamoto, etc.) are included. This is discussed in the context of their reaction mechanism, reaction dynamics, and whether and why resulting in an amorphous or crystalline product. This is followed by a discussion of different state-of-the art bottom-up synthesis methodologies, like solvothermal, interfacial, and solid-state synthesis. In the second part, the structure-property relationships in CC linked organic frameworks with representative examples of organocatalysis, photo(electro)catalysis, energy storage and conversion, magnetism, and molecular storage and separation are analyzed. The importance of linkage type, building blocks, topology, and crystallinity of the framework material in connection with the structure-property relationship is highlighted. Finally, brief concluding remarks are presented based on the key development of bottom-up synthetic methods and provide perspectives for future development in this field.

Construction of Porous Polyureas and Polyamides via Domino Polymerization and Their High-Efficiency Au(III) Adsorption.

The adoption of new synthesis strategy and monomers significantly promotes the construction of porous organic polymers (POPs) and their promising applications. A fabricating method of porous polyimides is developed via sequential imidization and cross-linking reaction among self-condensable building blocks, as reported in the authors' previous manuscript. Herein, porous polyureas (A-POPs) are prepared starting from 4-ethynylaniline and diisocyanate monomers, while porous polyamides (B-POPs) are synthesized from 4-ethynylbenzoic acid and diisocyanate monomers. It is found that decreasing the monomer content in solvent can effectively inhibit the premature phase separation and facilitate the evolution of integrated network. Eventually, a maximum surface area of 425 m2  g-1 is achieved for porous polyureas when the content of monomers is 10%. To the best knowledge, A-POPs are the porous polyureas with the highest surface areas reported up to now. The as-prepared porous polyurea (AN-POP) exhibits the maximum adsorption capacity of 1093.87 ± 5.23 mg g-1 and removal rate of 99.96% for Au(III), due to its high surface area and the coordination between the heteroatoms (N and O) in A-POPs and metal ions. Besides, the porous polyurea also exhibits excellent renewable efficiency and high selectivity to Au(III).

Building Porous Ni(Salen)-Based Catalysts from Waste Styrofoam via Autocatalytic Coupling Chemistry for Heterogeneous Oxidation with Molecular Oxygen.

The development of robust and industrially viable catalysts from plastic waste is of great significance, and the facile construction of high performance heterogeneous catalyst systems for phenol-quinone conversions remains a grand challenge. Herein, a feasible strategy is demonstrated to reclaim Styrofoam into hierarchically porous nickel-salen-loaded hypercrosslinked polystyrene (PS@Ni-salen) catalysts with high activities through an unusual autocatalytic coupling route. The salen is immobilized onto PS chain by Friedel-Crafts alkylation of benzyl chloride derivatives, and the generated hydrogen chloride coordinately promotes the simultaneous crosslinking and bridge formation between aromatic rings via a Scholl coupling route, leading to hierarchically porous networks. After the metallization with Ni, the resultant networks exhibit high catalytic activity for the oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone under mild conditions (303 K, 1 bar of O2 ). This catalyst also demonstrates attractive recycling performance without an obvious loss of catalytic efficiency over five consecutive cycles. This methodology might provide a potential sustainable alternative to construct environmentally benign and cost-effective catalysts for specific organic transformation.

Pyridinium-Functionalized Ionic Porous Organic Polymer for Rapid Scavenging of Oxoanions from Water.

Metal oxoanions adversely affect the food chain through bioaccumulation and biomagnification. Therefore, they are among the major freshwater contaminants that require immediate remediation. Although several adsorbents are developed over the years for sequestering these micropollutants, the selective removal of oxoanions remains still a formidable challenge. Herein, pyridinium and triazine-based ionic porous organic polymer, iPOP-Cl, developed through a Brønsted acid-catalyzed aminal formation reaction, is reported as a suitable anion exchange material for the selective removal of metal oxoanions from wastewater. The positively charged nitrogen centers, along with exchangeable chloride counter-ions in the porous polymer, allow facile oxoanion uptake. iPOP-Cl is found to be a selective scavenger of permanganate (MnO4 - ) and dichromate (Cr2 O7 2- ) from water in the presence of a high concentration of competing anions generally found in brackish water. The material exhibits fast sorption kinetics, a high uptake capacity (333 mg g-1 for MnO4 - and 358 mg g-1 for Cr2 O7 2- ), and excellent recyclability.

Rational Construction of Electrically Conductive Covalent Organic Frameworks through Encapsulating Fullerene via Donor-Acceptor Interaction.

A new kind of perylene-based 2D covalent organic framework (COF) is designed and synthesized based on the C2 + C2 topological diagram. The perylene-based COF is constructed via the condensation reaction using 2,5,8,11-tetrakis((4-formylphenyl) perylene (TFPPer) and 2,5,8,11-tetrakis(4-aminophenyl) perylene (TAPPer) as building blocks. The resulting TFPPer-TAPPer-COF features high crystallinity, excellent stability, intrinsic porosity, and an electron-rich skeleton. Significantly, the electrical performance of the COF can be enhanced through the encapsulation of fullerene (C60 ) into the 1D channels via donor-acceptor interaction. Compared to the pristine COF, the electrical conductivity of C60 @TFPPer-TAPPer-COF can be greatly increased from 8.98 × 10-8 to 1.59 × 10-5 S cm-1 , meanwhile the carrier mobility rises from 1.04 × 10-3 to 4.23 × 10-2 cm2 V-1 s-1 . The improvement in electrical performance stems from the strong donor-acceptor interaction between perylene and C60 . These results provide insights into the rational construction of conductive COFs through donor-acceptor interaction and demonstrate their great potential in related application fields.

Porphyrin/phthalocyanine-based porous organic polymers for pollutant removal and detection: Synthesis, mechanisms, and challenges.

The growing global concern about environmental threats due to environmental pollution requires the development of environmentally friendly and efficient removal/detection materials and methods. Porphyrin/phthalocyanine (Por/Pc) based porous organic polymers (POPs) as a newly emerging porous material are prepared through polymerizing building blocks with different structures. Benefiting from the high porosity, adjustable pore structure, and enzyme-like activities, the Por/Pc-POPs can be the ideal platform to study the removal and detection of pollutants. However, a systematic summary of their application in environmental treatment is still lacking to date. In this review, the development of various Por/Pc-POPs for pollutant removal and detection applications over the past decade was systematically addressed for the first time to offer valuable guidance on environmental remediation through the utilization of Por/Pc-POPs. This review is divided into two sections (pollutants removal and detection) focusing on Por/Pc-POPs for organic, inorganic, and gaseous pollutants adsorption, photodegradation, and chemosensing, respectively. The related removal and sensing mechanisms are also discussed, and the methods to improve removal and detection efficiency and selectivity are also summarized. For the future practical application of Por/Pc-POPs, this review provides the emerging research directions and their application possibility and challenges in the removal and detection of pollutants.

Synthesis of Pillar[5]arene- and Phosphazene-Linked Porous Organic Polymers for Highly Efficient Adsorption of Uranium.

It is crucial to design efficient adsorbents for uranium from natural seawater with wide adaptability, effectiveness, and environmental safety. Porous organic polymers (POPs) provide superb tunable porosity and stability among developed porous materials. In this work, two new POPs, i.e., HCCP-P5-1 and HCCP-P5-2 were rationally designed and constructed by linked with macrocyclic pillar[5]arene as the monomer and hexachlorophosphate as the core via a macrocycle-to-framework strategy. Both pillar[5]arene-containing POPs exhibited high uranium adsorption capacity compared with previously reported macrocycle-free counterparts. The isothermal adsorption curves and kinetic studies showed that the adsorption of POPs on uranium was consistent with the Langmuir model and the pseudo-second-order kinetic model. Especially, HCCP-P5-1 has reached 537.81 mg/g, which is greater than most POPs that have been reported. Meanwhile, the comparison between both HCCP-P5-1 and HCCP-P5-2 can illustrate that the adsorption capacity and stability could be adjusted by the monomer ratio. This work provides a new idea for the design and construction of uranium adsorbents from macrocycle-derived POPs.

Molecular Design of Porous Organic Polymer-Derived Carbonaceous Electrocatalysts for Pinpointing Active Sites in Oxygen Reduction Reaction.

The widespread application of fuel cells is hampered by the sluggish kinetics of the oxygen reduction reaction (ORR), which traditionally necessitates the use of high-cost platinum group metal catalysts. The indispensability of these metal catalysts stems from their ability to overcome kinetic barriers, but their high cost and scarcity necessitate alternative strategies. In this context, porous organic polymers (POPs), which are built up from the molecular level, are emerging as promising precursors to produce carbonaceous catalysts owning to their cost-effectiveness, high electrical conductivity, abundant active sites and extensive surface area accessibility. To enhance the intrinsic ORR activity and optimize the performance of these electrocatalysts, recognizing, designing, and increasing the density of active sites are identified as three crucial steps. These steps, which form the core of our review, serve to elucidate the link between the material structure design and ORR performance evaluation, thereby providing valuable insights for ongoing research in the field. Leveraging the precision of polymer skeletons based on molecular units, POP-derived carbonaceous catalysts provide an excellent platform for in-depth exploration of the role and working mechanism for the specific active site during the ORR process. In this review, the recent advances pertaining to the synthesis techniques and electrochemical functions of various types of active sites, pinpointed from POPs, are systematically summarized, including heteroatoms, surficial substituents and edge/defects. Notably, the structure-property relationship, between these active sites and ORR performance, are discussed and emphasized, which creates guidelines to shed light on the design of high-performance ORR electrocatalysts.

Porous Organic Polymers for Selective Palladium Recovery and Heterogeneous Catalysis.

Palladium (Pd) recycling from waste materials is an important approach in order to meet the growing demand for Pd originating from its broad range of applications including automotive industry, electronics and catalysis. In this article, we discuss the design principles of solid-sorbents for efficient recovery of Pd from waste sources with a particular emphasis on porous organic polymers (POPs), which emerged as promising porous materials for Pd recovery due to their tunable chemical functionality, stability and porosity. We discuss the critical role of binding sites and porosity in the Pd uptake capacity, adsorption kinetics and selectivity. We also highlight the use of captured Pd within the polymer networks as heterogeneous catalysts for cross-coupling reactions.