Symbiotically Reinforced Bimetallic Photocatalysis in Conjugated Metal−Organic Framework Nanosheets

Abstract

Compared to monometallic counterparts, bimetallic two‐dimensional conjugated metal‐organic framework (2D c‐MOF) nanosheets possess preferable metal tunability and synergistic effect for performance optimization, yet rarely developed in photocatalytic hydrogen evolution to date. In this study, a feasible post‐synthetic strategy of second metal installation (SMI) is proposed and applied to construct a crystalline bimetallic 2D c‐MOF nanosheet, HTHATN‐Ni‐Pt‐NS. HTHATN‐Ni‐Pt‐NS exhibits high electrical conductivity and efficient hydrogen evolution with the rate of 47.2 mmol g−1 h−1, which is 13.5‐fold higher than that of pristine HTHATN‐Ni‐NS without PtII decoration under visible light irradiation. Experimental and theoretical analysis reveal that introduction of low amount of PtII provides catalytically active metal sites and optimizes the ΔGH* value of NiII centers, thus resulting in the enhanced performance of proton reduction. This study represents the first example of symbiotic bimetallic centers in MOF nanosheets highlighting SMI strategy as an efficient approach to construct photocatalysts.

Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

“…32,33 While numerous MOFs have been explored for eCO 2 RR, only a limited few have exhibited noteworthy efficiency in catalyzing the conversion of CO 2 to EtOH. 34,35 In contrast to direct synthesis methods, postsynthetic modification (PSM) holds distinct advantages in fine-tuning catalytic activity and is frequently employed to precisely tailor material properties and functions. 36 Cu−HAB (HAB = hexaiminobenzene) stands out as a conductive two-dimensional (2D) π-conjugated MOF boasting an impressive electrical conductivity of 13 S cm −1 .…”

“…Metal–organic frameworks (MOFs) constitute a class of crystalline porous materials characterized by well-defined structures and versatile design possibilities. , Given their innate ability to modulate the microenvironment and coordination configurations of metal ions, MOFs have garnered significant attention in the realm of eCO 2 RR. , While numerous MOFs have been explored for eCO 2 RR, only a limited few have exhibited noteworthy efficiency in catalyzing the conversion of CO 2 to EtOH. , In contrast to direct synthesis methods, postsynthetic modification (PSM) holds distinct advantages in fine-tuning catalytic activity and is frequently employed to precisely tailor material properties and functions …”

2D Conductive Metal–Organic Frameworks for Electrochemical Energy Application

“…[1][2][3][4][5] By virtue of their unique hybrid structures combining inorganic and organic components, MOFs exhibit exceptional properties including high porosity, large specific surface areas (SSAs), abundant active sites, and tunable structures. Consequently, extensive applications in diverse fields such as gas storage and separation, [6][7][8][9] sensing, [10][11][12][13][14][15] catalysis, [16][17][18][19][20] spintronics, [21][22][23][24][25] batteries, [26][27][28][29][30] capacitors, [31][32][33][34] among others were explored. However, conventional MOFs typically suffer from low intrinsic conductivity (δ < 10 −10 S • cm −1 ), rendering them electrical insulators and limiting their potential in electrochemical applications.…”