Hierarchical heterostructure photocatalysts with broad spectrum solar light utilization, particularly in the near-infrared (NIR) region, are emerging classes of advanced photocatalytic materials for solar-driven CO₂ conversion into value-added chemical feedstocks. Herein, a novel two-demensional/three-demensional (2D/3D) hierarchical composite is hydrothermally synthesized by assembling vertically-aligned ZnIn₂S₄ (ZIS) nanowall arrays on nitrogen-doped graphene foams (NGF). The prepared ZIS/NGF composite shows enhancement in photothermal conversion ability and selective CO₂ capture as well as solar-driven CO₂ photoreduction. At 273 K and 1 atm, the ZIS/NGF composite with 1.0 wt% NGF achieves a comparably high CO₂-to-N₂ selectivity of 30.1, with an isosteric heat of CO₂ adsorption of 48.2 kJ mol⁻¹. And in the absence of cocatalysts and sacrificial agents, the ZIS/NGF composite with cyclability converts CO₂ into CH₄, CO and CH₃OH under simulated solar light illumination, with the respective evolution rates about 9.1, 3.5, and 5.9 times higher than that of the pristine ZIS. In-depth analysis using in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) in conjunction with Kelvin probe measurements reveals the underlying charge transfer pathway and process from ZIS to NGF.

具有广谱太阳光利用率的分层异质结构光催化剂，特别是在近红外（NIR）区域，是新兴的一类先进的光催化材料，用于将太阳光驱动的CO ₂转化为增值的化学原料。本文中，通过将垂直排列的ZnIn ₂ S ₄（ZIS）纳米壁阵列组装在掺氮石墨烯泡沫（NGF）上，水热合成了一种新型的二维/三维（2D / 3D）分层复合材料。制备的ZIS / NGF复合材料显示出光热转化能力和选择性CO ₂捕获以及太阳能驱动的CO _2的增强光还原。在273 K和1个大气压下，具有1.0 wt％NGF的ZIS / NGF复合材料可实现30.1的相对较高的CO ₂ -N ₂选择性，CO ₂吸附的等排热为48.2 kJ mol ^-1。在没有助催化剂和牺牲剂的情况下，具有可循环性的ZIS / NGF复合材料在模拟太阳光照射下将CO ₂转化为CH ₄，CO和CH ₃ OH，其各自的分解速率分别是其的9.1，3.5和5.9倍。原始的ZIS。使用原位进行深入分析 辐射X射线光电子能谱（ISI-XPS）结合开尔文探针测量揭示了从ZIS到NGF的潜在电荷转移途径和过程。