Li Jinglin, Sheng Bowen, Chen Yiqing, Sadaf Sharif Md, Yang Jiajia, Wang Ping, Pan Hu, Ma Tao, Zhu Lei, Song Jun, Lin He, Wang Xinqiang, Huang Zhen, Zhou Baowen
Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
State Key Laboratory of Artificial Microstructure and Mesoscopic Physics, School of Physics, Nano-Optoelectronics Frontier Center of Ministry of Education (NFC-MOE), Peking University, Beijing, 10087, China.
Commun Chem. 2022 Sep 6;5(1):107. doi: 10.1038/s42004-022-00728-x.
Upcycling of carbon dioxide towards fuels and value-added chemicals poses an opportunity to overcome challenges faced by depleting fossil fuels and climate change. Herein, combining highly controllable molecular beam epitaxy growth of gallium nitride (GaN) under a nitrogen-rich atmosphere with subsequent air annealing, a tunable platform of gallium oxynitride (GaNO) nanowires is built to anchor rhodium (Rh) nanoparticles for carbon dioxide hydrogenation. By correlatively employing various spectroscopic and microscopic characterizations, as well as density functional theory calculations, it is revealed that the engineered oxynitride surface of GaN works in synergy with Rh to achieve a dramatically reduced energy barrier. Meanwhile, the potential-determining step is switched from *COOH formation into *CO desorption. As a result, significantly improved CO activity of 127 mmol‧g‧h is achieved with high selectivity of >94% at 290 °C under atmospheric pressure, which is three orders of magnitude higher than that of commercial Rh/AlO. Furthermore, capitalizing on the high dispersion of the Rh species, the architecture illustrates a decent turnover frequency of 270 mol CO per mol Rh per hour over 9 cycles of operation. This work presents a viable strategy for promoting CO refining via surface engineering of an advanced support, in collaboration with a suitable metal cocatalyst.
将二氧化碳升级转化为燃料和增值化学品为克服化石燃料枯竭和气候变化所带来的挑战提供了契机。在此，通过在富氮气氛下结合氮化镓（GaN）的高度可控分子束外延生长以及随后的空气退火，构建了一个氮氧化镓（GaNO）纳米线的可调谐平台，用于锚定铑（Rh）纳米颗粒以进行二氧化碳加氢。通过相关地采用各种光谱和显微镜表征以及密度泛函理论计算，揭示了工程化的GaN氮氧化物表面与Rh协同作用，实现了显著降低的能垒。同时，决定电位步骤从COOH形成转变为CO脱附。结果，在290°C和大气压下，CO活性显著提高至127 mmol‧g‧h，选择性高于94%，比商业Rh/AlO高出三个数量级。此外，利用Rh物种的高分散性，该结构在9个操作循环中展示了每摩尔Rh每小时270摩尔CO的良好周转频率。这项工作提出了一种可行的策略，即通过先进载体的表面工程与合适的金属助催化剂协作来促进CO精炼。
