Supramolecular preorganization effect to access single cobalt sites for enhanced photocatalytic hydrogen evolution and nitrogen fixation

Zhang，Wenyao1,2; Fu，Yongsheng1; Peng，Qiong1; Yao，Qiushi3; Wang，Xin1; Yu，Aiping2; Chen，Zhongwei2

2020-08-15

10.1016/j.cej.2020.124822

CHEMICAL ENGINEERING JOURNAL   影响因子和分区

1385-8947

1873-3212

Ever-increased investigation has been focused on designing photocatalysts comprising intimately interfaced photo-absorbers and co-catalysts for promoting the separation of electron-hole pairs and surface redox reaction. Herein, we present a photocatalytic system in which the single-site-cobalt-atom is firmly trapped and stabilized into the frameworks of porous crimped graphitic carbon nitride (g-CN), proposing as advanced photocatalysts for solar-photon-driven hydrogen production and nitrogen fixation. A single molecular source of dicyandiamide was used to partly transformed and then in-situ preorganized into supermolecular precursor, which could coordinate with cobalt ions and manipulate the interactions under elevated temperature prior to the condensation to form atomically Co dispersed g-CN materials. Theoretical evaluation and experimental validation identified that the chemical integration of single-site-cobalt-atom on g-CN is critical in optimizing the electron and band structures and accelerating the interfacial charge transfer process. As a result, the as-obtained Co@g-CN possesses an exceptional photocatalytic hydrogen production rate (2481 μmolhg, λ > 420 nm) and conspicuous nitrogen photofixation performances under visible-light irradiation. Such concerted catalysis attributes to the negative shift of the Fermi level in Co@g-CN system deriving from the induced charge-transfer effect, which effectively gains the reducibility of electrons and creates more active sites for photocatalytic reactions.

Graphitic carbon nitride Photocatalytic hydrogen evolution Photocatalytic nitrogen fixation Single-atom catalyst Supramolecular Synergistic active centers

SCI ; EI

英语

其他

National Natural Science Foundation of China[51772156][51872144] ; Natural Science Foundation of Jiangsu Province[BK20180019][BK20171423] ; Fundamental Research Funds for the Central Universities[30917015102][30918014103]

Engineering

Engineering, Environmental ; Engineering, Chemical

WOS:000540937000005

ELSEVIER SCIENCE SA

20201508391372

Atoms ; Cobalt ; Redox reactions ; Hydrogen production ; Solar power generation ; Charge transfer ; Nitrogen fixation ; Supramolecular chemistry ; Surface reactions

Gas Fuels:522 ; Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Solar Power:615.2 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Atomic and Molecular Physics:931.3

ENGINEERING

2-s2.0-85082743206

Scopus

1.Key Laboratory of Soft Chemistry and Functional Materials,Nanjing University of Science and Technology,Ministry of Education,Nanjing,210094,China
2.Waterloo Institute for Nanotechnology,University of Waterloo,Waterloo,N2L3G1,Canada
3.Department of Physics,Southern University of Science and Technology,Shenzhen,518055,China

Zhang，Wenyao,Fu，Yongsheng,Peng，Qiong,et al. Supramolecular preorganization effect to access single cobalt sites for enhanced photocatalytic hydrogen evolution and nitrogen fixation[J]. CHEMICAL ENGINEERING JOURNAL,2020,394.

Zhang，Wenyao.,Fu，Yongsheng.,Peng，Qiong.,Yao，Qiushi.,Wang，Xin.,...&Chen，Zhongwei.(2020).Supramolecular preorganization effect to access single cobalt sites for enhanced photocatalytic hydrogen evolution and nitrogen fixation.CHEMICAL ENGINEERING JOURNAL,394.

Zhang，Wenyao,et al."Supramolecular preorganization effect to access single cobalt sites for enhanced photocatalytic hydrogen evolution and nitrogen fixation".CHEMICAL ENGINEERING JOURNAL 394(2020).