Numpilai Thanapha, Polsomboon Nutkamaithorn, Dolsiririttigul Napaphut, Jitapunkul Kulpavee, Donphai Waleeporn, Imyen Thidarat, Chareonpanich Metta, Witoon Thongthai
Department of Environmental Science, Faculty of Science and Technology, Thammasat University, Pathumthani, 12120, Thailand.
Center of Excellence on Advanced Adsorbents and Catalysts for Carbon Capture and Utilization, Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, Thailand.
ACS Omega. 2025 May 13;10(20):20886-20894. doi: 10.1021/acsomega.5c02289. eCollection 2025 May 27.
This study evaluates the catalytic performance of ZnO/ZrO catalysts, which were synthesized through reverse co-precipitation with Zn/(Zn + Zr) ratios varying from 0 to 100%, for converting CO into methanol (CHOH). The catalysts underwent systematic characterization using XRD, TEM-EDS mapping, N adsorption-desorption, XPS, and TPD-MS techniques, focusing on both H and CO interactions. Results showed that pure ZnO typically forms as aggregated needles, while pure ZrO manifests as clustered aggregates of significantly smaller nanoparticles. At lower Zn contents (20-30%), ZnO particles are small and evenly distributed among the ZrO nanoparticles, effectively inhibiting ZrO aggregation. Conversely, at higher Zn contents (40-80%), ZnO particles increase in size, while ZrO particles remain smaller and tend to accumulate predominantly on the surfaces of the larger ZnO particles. Catalysts with a predominance of ZnO contents exhibited greater H adsorption, whereas those with higher ZrO contents showed increased CO adsorption. The Zn60Zr40 (60 wt % Zn) catalyst was identified as optimal, achieving 11.8% CO conversion at 340 °C, with a peak CHOH selectivity of 74.0% at 320 °C and a CHOH yield of 6.1% at 340 °C, maintaining excellent stability over 100 h. Furthermore, the study found a direct correlation between catalytic activity and gas adsorption: higher H adsorption rates significantly improved CO conversion, while CHOH selectivity was more influenced by CO adsorption. These findings underscore the importance of adsorptive properties in determining product distribution and offer essential insights for designing ZnO/ZrO catalysts optimized for efficient CHOH production from CO hydrogenation.
本研究评估了通过反向共沉淀法合成的ZnO/ZrO催化剂的催化性能，其中Zn/(Zn + Zr)的比例从0到100%不等，用于将CO转化为甲醇（CHOH）。使用XRD、TEM-EDS映射、N吸附-脱附、XPS和TPD-MS技术对催化剂进行了系统表征，重点关注H和CO的相互作用。结果表明，纯ZnO通常形成聚集的针状，而纯ZrO则表现为明显更小的纳米颗粒的聚集聚集体。在较低的Zn含量（20-30%）下，ZnO颗粒较小且均匀分布在ZrO纳米颗粒之间，有效抑制了ZrO的聚集。相反，在较高的Zn含量（40-80%）下，ZnO颗粒尺寸增大，而ZrO颗粒保持较小并倾向于主要聚集在较大的ZnO颗粒表面。以ZnO含量为主的催化剂表现出更大的H吸附，而ZrO含量较高的催化剂则表现出CO吸附增加。Zn60Zr40（60 wt% Zn）催化剂被确定为最佳催化剂，在340°C时实现了11.8%的CO转化率，在320°C时CHOH选择性峰值为74.0%，在340°C时CHOH产率为6.1%，在100小时内保持优异的稳定性。此外，该研究发现催化活性与气体吸附之间存在直接相关性：较高的H吸附速率显著提高了CO转化率，而CHOH选择性受CO吸附的影响更大。这些发现强调了吸附性能在确定产物分布中的重要性，并为设计用于通过CO加氢高效生产CHOH的ZnO/ZrO催化剂提供了重要见解。
