Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently bonded organic cages can assemble into crystalline microporous materials. The porosity is prefabricated and intrinsic to the molecular cage structure, as opposed to being formed by non-covalent self-assembly of non-porous sub-units. The three-dimensional connectivity between the cage windows is controlled by varying the chemical functionality such that either non-porous or permanently porous assemblies can be produced. Surface areas and gas uptakes for the latter exceed comparable molecular solids. One of the cages can be converted by recrystallization to produce either porous or non-porous polymorphs with apparent Brunauer-Emmett-Teller surface areas of 550 and 23 m2 g(-1), respectively. These results suggest design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores.

Photocatalytic hydrogen production from water offers an abundant, clean fuel source, but it is challenging to produce photocatalysts that use the solar spectrum effectively. Many hydrogen-evolving photocatalysts are active in the ultraviolet range, but ultraviolet light accounts for only 3% of the energy available in the solar spectrum at ground level. Solid-state crystalline photocatalysts have light absorption profiles that are a discrete function of their crystalline phase and that are not always tunable. Here, we prepare a series of amorphous, microporous organic polymers with exquisite synthetic control over the optical gap in the range 1.94-2.95 eV. Specific monomer compositions give polymers that are robust and effective photocatalysts for the evolution of hydrogen from water in the presence of a sacrificial electron donor, without the apparent need for an added metal cocatalyst. Remarkably, unlike other organic systems, the best performing polymer is only photoactive under visible rather than ultraviolet irradiation.

No abstract

Covalent triazine frameworks (CTFs) are normally synthesized by ionothermal methods.T he harsh synthetic conditions and associated limited structural diversity do not benefit for further development and practical large-scale synthesis of CTFs.Herein we report anew strategy to construct CTFs (CTF-HUSTs) via apolycondensation approach,which allows the synthesis of CTFs under mild conditions from aw ide arrayo fb uilding blocks.I nterestingly,t hese CTFs displayalayered structure.T he CTFs synthesized were also readily scaled up to gram quantities.T he CTFs are potential candidates for separations,p hotocatalysis and for energy storage applications.I np articular,C TF-HUSTs are found to be promising photocatalysts for sacrificial photocatalytic hydrogen evolution with am aximum rate of 2647 mmol h À1 g À1 under visible light. We also applied ap yro-lyzed form of CTF-HUST-4 as an anode material in asodium-ion battery achieving an excellent discharge capacity of 467 mAh g À1. Covalent organic frameworks (COFs) are an emerging class of porous materials,characterized by their ordered structures, high surface areas,and structural diversity. [1] They have shown promise in applications such as gas adsorption, [2] catalysis, [3] and optoelectronics. [4] Av ariety of methods have been reported to prepare COFs,s uch as polycondensation, [1a, 4a] cyclization reactions, [5] or surface mediated methods. [1b, 6] Covalent triazine frameworks (CTFs) are related to COFs and are typically constructed through cyclization reaction of nitrile aromatic building blocks;t hey feature high physico-chemical stability and high nitrogen content. [5, 7] Because of these characteristics,CTFs have found diverse applications in gas adsorption and storage, [5a, 7a,b] catalysis, [7c-e] and energy storage. [7f,g] There are still, however, al imited number of approaches for the synthesis of CTFs. [5a, 7a] Themost common approach is ionothermal synthesis at high temperatures (! 400 8 8C), which also requires alarge amount of ZnCl 2 to serve as both catalyst and reaction medium. [5a] This method can lead to CTFs with ad egree of crystalline order,b ut the high reaction temperatures cause the partial carbonization of the structure and the materials are obtained in the form of black powders.H ence,C TFs prepared by this method lack an electronic band gap and may be unsuitable for photophysical applications.F urthermore,t hese reaction temperatures consume alarge amount of energy and preclude all but the most stable building blocks,thus limiting the scope for scale up and synthetic diversity.I ti s, therefore,i mperative to find new methods for the synthesis of CTFs under milder conditions. Previous research has shown that CTFs could be synthesized at room temperature,a nd catalyzed by strong and corrosive acid such as trifluoromethylsufonic acid. [7a,b] This avoids carbonization, but the method is obviously not suitable to acid-sensitive building blocks,and also the resulting materials did not have layered structures. Here,wedevelop anew strategy involvi...

We demonstrate a generic new approach to produce homogeneous and reproducible hydrogels from low molecular weight hydrogelators using the controlled hydrolysis of glucono-d-lactone (GdL). GdL slowly hydrolyses in water to give gluconic acid, which controllably lowers the pH. This hydrolysis is slower than the rate of dissolution; hence uniform pH change throughout the sample is possible. This results in homogeneous hydrogels that are unaffected by their shear or mixing history. A further advantage of this method is that it allows the gelation process to be monitored, giving further insight into the mechanism by which gelation occurs.