Nickel Metal–Organic Framework Monolayers for Photoreduction of Diluted CO₂: Metal‐Node‐Dependent Activity and Selectivity

Abstract

Photocatalytic conversion of diluted CO2 into solar fuel is highly appealing yet still in its infancy. Herein, we demonstrate the metal‐node‐dependent performance for photoreduction of diluted CO2 by constructing Ni metal–organic framework (MOF) monolayers (Ni MOLs). In diluted CO2 (10 %), Ni MOLs exhibit a highest apparent quantum yield of 1.96 % with a CO selectivity of 96.8 %, which not only exceeds reported systems in diluted CO2 but also is superior to most catalysts in pure CO2. Whereas isostructural Co MOLs is almost inactive in diluted CO2, indicating the performance is dependent on the metal nodes. Experimental and theoretical investigations show that strong CO2 binding affinity of Ni MOLs is the crucial factor, which stabilizes the Ni‐CO2 adducts and facilitates CO2‐to‐CO conversion.

Spinel‐Type Mixed Metal Sulfide NiCo2S4 for Efficient Photocatalytic Reduction of CO2 with Visible Light

“…CO is detected as the sole CO 2 reduction product, coupled with a small amount of H 2 . No any other CO 2 reduction products (e. g., HCOOH, CHOH, CH 3 OH and CH 4 ) are detected in the system, which is in agreement with the results of previous works . Such a product distribution may be attributed to lower conduction band potential of NiCo 2 S 4 .…”

“…No any other CO 2 reduction products (e. g., HCOOH, CHOH, CH 3 OH and CH 4 ) are detected in the system, which is in agreement with the results of previous works. [18,26,33,36] Such a product distribution may be attributed to lower conduction band potential of NiCo 2 S 4 . To be specific, the formation of CH 4 and other hydrocarbon products typically proceeds via a series of elementary steps with CO as the intermediate, involving transfer of an electron in most of the steps.…”

“…The efficient CO 2 photoreduction systems are typically composed of several modules, such as light harvesters, electron mediator, CO 2 activators and their desired integration, to operate the reaction through a tandem manner. [24][25][26][27] Nickel and cobalt species with rich redox states have been demonstrated to be active sites of photocatalysts, which can powerfully promote the separation and transfer of light-excited charges of CO 2 photoconversion catalysis. [18,[26][27][28][29][30][31] When the reduction reaction is further coupled with the protons, reinforced performance of CO 2 photoreduction can be achieved.…”

Encapsulating Perovskite Quantum Dots in Iron‐Based Metal–Organic Frameworks (MOFs) for Efficient Photocatalytic CO2 Reduction

“…[1][2][3][4][5][6] In the artificial photosynthesis process,acrucial challenge is to design efficient and low-cost catalysts and photosensitizers.I nt his context, as eries of efficient photocatalysts based on earth-abundant elements,s uch as Fe, [7][8][9] Co [10][11][12][13] and Ni [14,15] have been developed. [1][2][3][4][5][6] In the artificial photosynthesis process,acrucial challenge is to design efficient and low-cost catalysts and photosensitizers.I nt his context, as eries of efficient photocatalysts based on earth-abundant elements,s uch as Fe, [7][8][9] Co [10][11][12][13] and Ni [14,15] have been developed.…”

“…Using water as an electron source,MAPbI 3 @PCN-221(Fe 0.2 )e xhibits ar ecord-high total yield of 1559 mmol g À1 for photocatalytic CO 2 reduction to CO (34 %) and CH 4 (66 %), 38 times higher than that of PCN-221(Fe 0.2 )i nt he absence of perovskite QDs.Direct light-driven CO 2 reduction to high-value added chemical feedstocks or fuels using efficient catalysts is one of fascinating technologies,i nr esponse to slowly but inevitably exhausted fossil fuels,aswell as the climate-changing induced by CO 2 greenhouse gas emission. [1][2][3][4][5][6] In the artificial photosynthesis process,acrucial challenge is to design efficient and low-cost catalysts and photosensitizers.I nt his context, as eries of efficient photocatalysts based on earth-abundant elements,s uch as Fe, [7][8][9] Co [10][11][12][13] and Ni [14,15] have been developed. [16] Meanwhile,s ome semiconductor nanocrystals (NCs) have been pursued as photosensitizers,o wing to their large extinction coefficients and flexibly adjustable thermodynamic and optical properties with the regulation of particle sizes.…”