Selective CO2-to-Formate Conversion Driven by Visible Light over a Precious-Metal-Free Nonporous Coordination Polymer
Selective CO2-to-Formate Conversion Driven by Visible Light over a Precious-Metal-Free Nonporous Coordination Polymer
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DOI：
10.1021/acscatal.2c02177
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发表时间：
2022-08
期刊：
影响因子：
12.9
通讯作者：
Y. Kamakura;Shuhei Yasuda;Naoki Hosokawa;Shunta Nishioka;Sawa Hongo;T. Yokoi;D. Tanaka;K. Maeda
中科院分区：
文献类型：
--
作者：
Y. Kamakura;Shuhei Yasuda;Naoki Hosokawa;Shunta Nishioka;Sawa Hongo;T. Yokoi;D. Tanaka;K. Maeda
金属有机骨架（MOFs）和配位聚合物（CPs）由于其电子和结构性质的高可调性而成为高性能光催化剂的潜在候选者。例如，mof和CPs具有高比表面积（~ 1000 m2g-1），已被用作可见光驱动的光催化剂，用于二氧化碳还原和水分解。在这里，我们展示了一个独特的CP，它与地球上丰富的金属离子Pb2+具有金属硫键。与普通的高表面积mof和CPs不同，这种CP是无孔的，只有0.7 m2g - 1的表面积。然而，由于其吸收可见光至~ 500 nm的能力，它在可见光照射下有效地光催化co2还原成甲酸（HCOO -），选择性为bbb99 %，在400 nm处的表观量子产率为2.6%，即使没有后处理，如负载助催化剂。这些值是迄今为止报道的无贵金属单组分光催化剂在可见光驱动下将co2还原为HCOO -的最高值。因此，这项工作可能揭示了无孔CPs作为光催化co2转化系统构建单元的巨大潜力。
Metal–organic frameworks (MOFs) and coordination polymers (CPs) are potential candidates for high-performance photocatalysts because of their high tunability of electronic and structural properties. For example, MOFs and CPs having a high specific surface area (∼1000 m2g–1) have been applied as visible-light-driven photocatalysts for CO2reduction and water splitting. Herein, we show a unique CP possessing a metal–sulfur bond with Pb2+, an earth-abundant metal ion. Different from ordinary high-surface-area MOFs and CPs, this CP is nonporous and has just 0.7 m2g–1surface area. Nevertheless, owing to its capability of absorbing visible light up to ∼500 nm, it efficiently photocatalyzes CO2reduction to formate (HCOO–) under visible-light irradiation with >99% selectivity and an apparent quantum yield of 2.6% at 400 nm, even without postmodification treatment such as cocatalyst loading. These values are the highest yet reported for a precious-metal-free single-component photocatalyst for the visible-light-driven reduction of CO2to HCOO–. This work may thus shed light on the great potential of nonporous CPs as building units of photocatalytic CO2conversion systems.