An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

Abstract

electronic structure. [3][4][5] Nevertheless, most inorganic photocatalysts suffer from low activity under visible light, complexity in the preparation, and the limited natural resources. Recent studies demonstrated that organic semiconductors could be a promising class of photocatalysts for hydrogen evolution because of their diverse structures, various synthetic strategies, and tunable electronic properties. [6][7][8] To date, various organic polymers with conjugated skeletons have been developed as photocatalysts for hydrogen evolution. [9][10][11] In particular, significant advances in the preparation of conjugated microporous polymer (CMP) photocatalysts with high photocatalytic activity have been achieved. [12][13][14] Many studies revealed that designing a donor-acceptor (D-A) molecular structure is an efficient strategy to boost the photocatalytic activity of conjugated polymer photocatalysts, [15][16][17][18] since the intrinsic electron push-pull effect in a D-A conjugated polymer could promote the separation of light-induced hole/ electron. The nature of electron donor and acceptor units plays a key point in the charges transfer and separation, which affect significantly the photocatalytic activity. Therefore, the selection of electron donor and acceptor is of great importance for constructing organic polymer photocatalysts with high photocatalytic activity. In general, aromatic heterocyclic compounds with narrow band gap are commonly used as electron acceptors, and aromatic hydrocarbons with delocalized π-electron are employed as electron donors to build D-A type polymer photocatalysts. Based on the developed D-A polymer photo catalysts to date, [15,[19][20][21][22] dibenzo[b,d]thiophene-S,S-dioxide (BTDO) might be the most effective acceptor unit due to its strong electronwithdrawing capability and high hydrophilicity, [23][24][25] and pyrene with planar molecular structure and large delocalized π-electron system is the most effective electron donor to prepare high performance polymer photocatalysts. [26,27] Although there have been significant advances in the photo catalytic activity of polymer photocatalysts by structure optimization, [28,29] the limited scope of high efficient electron donors and acceptors hinders the further development of organic polymer photo catalysts. To further improve the photocatalytic activity and enrich the D-A) molecular structure show high photocatalytic activity for hydrogen evolution due to the efficient light-induced electron/hole separation, which is mostly determined by the nature of electron donor and acceptor units. Therefore, the selection of electron donor and acceptor holds the key point to construct high performance polymer photocatalysts. Herein, two dibenzo[b,d]thiophene-S,Sdioxide (BTDO) containing CMP photocatalysts using tetraphenylethylene (TPE) or dibenzo[g,p]chrysene (DBC) as the electron donor to investigate the influence of the geometry of electron donor on the photocatalytic activity are design and synthesized. Compared with the twisted TPE donor,...

Facile metal-free synthesis of pyrrolo[3,2-b]pyrrolyl-based conjugated microporous polymers for high-performance photocatalytic degradation of organic pollutants

“…It has been reported that the longer the π-electron conjugated system, the better charge separation and transfer efficiency. 56,78,84 Together, these findings confirmed that our Py-CMPs had good ability to separate and transfer photogenerated electrons under illumination.…”

Rational Design of Conjugated Microporous Polymer Photocatalysts with Definite D−π–A Structures for Ultrahigh Photocatalytic Hydrogen Evolution Activity under Natural Sunlight

“…The photocatalytic H 2 generation experiment was conducted on an all-glass automatic online trace gas analysis system (Labsolar-6A, Beijing Perfectlight Technology Co., Ltd.) according to our previously reported procedures. 34…”

RuS2@CN-x with exposed (200) facet as a high-performance photocatalyst for selective C–C bond cleavage of biomass coupling with H–O bond cleavage of water to co-produce chemicals and H2

“…Meanwhile, the high price and limited precious metal resources increase the cost of this technology and hinder its large-scale application and promotion. Therefore, many scholars have gradually turned their attention to the photocatalytic hydrogen evolution technology, [12][13][14][15] which is a low-energy consumption and environmentally friendly method. In addition, the technology is easier to build and expand.…”