Atomically Thin Zn₂GeO₄ Nanoribbons: Facile Synthesis and Selective Photocatalytic CO₂ Reduction toward CO

Abstract

Atomically thin Zn 2 GeO 4 (ZGO) nanoribbons exclusively exposing the {100} facet of ∼1 nm in thickness were successfully prepared via convenient photo-oxidation exfoliation of the ZGO−ethylenediamine hybrid at room temperature. The ultrathin ZGO nanoribbons [abbreviated as ZGO(100)] exhibit efficient and dominantly selective CO 2 photoreduction performance into CO with the evolution yield of up to 20.81 μmol g −1 h −1 in the presence of water vapor, in much contrast to only CH 4 production of 0.67 μmol g −1 h −1 for (010), exposing the thick ZGO nanobelts reported previously. The atomically thin structure of ZGO(100) shortens the migration distance of charge carriers onto the surface from the interior and allows more electrons to survive and accumulate on the surface, thus benefiting the activation and reduction of CO 2 . The density function theory calculation reveals that the formed CO* is inclined to escape from the exclusively exposed {100} facet of the ultrathin ZGO nanoribbon rather than be further protonated to derive CHO*, a vital intermediate for CH 4 formation, leading ZGO(100) to be an ideal platform for catalytically selective CO production. This work would not only enrich atomically thin catalyst materials but also render a new platform for the development of ternary semiconductors with outstanding performance in CO 2 photoconversion.

Stable CO2 reduction under natural air on Ni–Sn hydroxide photocatalyst with dynamic renewable oxygen vacancies

“…The former was assigned to the COO − species [36][37][38]. Numerous reports revealed that COOH * was the important intermediate for the CO product, which converted to * CO by accepting coupled proton and electron with releasing one H 2 O molecule [8,39,40]. The latter was due to the symmetric vibration of a bidentate CO 3 2− (v s (OCO)), commonly formed by the reaction of CO 2 with dual sites of surface oxygen and metallic atoms [41][42][43].…”

“…To date, certain achievements have been made in improving the conversion efficiency based on photocatalyst development through hybrid semiconductors, morphology regulation, and surface modification [4][5][6]. However, current investigations were focused on the high-concentration system, which highly relied on the processes involving capture, sequestration, and transport that consumed time, labor, and energy [7,8]. Considering the nature photosynthesis, it is vital to develop an advanced photocatalyst with a stable ability to deal with the CO 2 reduction reaction (CO 2 RR) with low concentration direct from natural air.…”

Comprehensive Insight into Construction of Active Sites toward Steering Photocatalytic CO2 Conversion

“…DFT reveals that the formed CO* is inclined to escape from the exclusively exposed (100) facet other than further protonation, leading catalytically selective CO production. [66] The high-index facets possesses a high density of surface steps and kinks with low-coordination numbers, which may exhibit extraordinary photocatalytic performance. [93] NH 2 -MIL-125(Ti) with exposed high-index (112) facets displays superior activity for CO 2 -to-CO and CH 4 conversions, which are 33 and 31 times higher for CO and CH 4 productions than the (001)/(111) facets.…”

“…DFT reveals that the formed CO* is inclined to escape from the exclusively exposed (100) facet other than further protonation, leading catalytically selective CO production. [ 66 ]…”

Tandem catalysts CuSe/AuX for increasing local *CO concentration to promote the photocatalytic CO2 reduction to C2H4

“…A series of intricate chemical processes is indispensable to convert CO 2 and realize turning "waste" into a treasure. At present, CO 2 reduction reaction (CO 2 RR) products can be divided into CO, [5][6][7][8] CH 4 , [9][10][11] CH 3 OH, [12][13][14] HCOOH, [15][16][17] C 2 H 4 , [18][19][20][21] C 2 H 5 OH 22 , and some other chemical compounds 23,24 according to the types of catalysts. Among them, C 2 H 4 has garnered significant attention from researchers for its versatility and usefulness as a raw material in the synthesis of many chemicals.…”