{"title":"了解二氧化碳加氢模型 ZrOx/Au (111) 催化剂的形态和化学活性","authors":"","doi":"10.1016/j.susc.2024.122590","DOIUrl":null,"url":null,"abstract":"<div><p>In this study, the growth of ZrO<sub>x</sub> on Au (111) was investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Nanostructures of ZrO<sub>x</sub> (<em>x</em> = 1,2) at the sub-monolayer (≤ 0.3 ML) level were prepared by vapor depositing Zr metal onto Au (111) followed by oxidation with O<sub>2</sub> or CO<sub>2</sub>. At low coverages of the admetal (< 0.05 ML), the formed ZrO<sub>x</sub> nanostructures were dispersed randomly on the terraces and steps of the Au(111) substrate. Strong oxide-metal interactions prevented the formation of islands of zirconia. The ZrO<sub>x</sub> nanostructures displayed a reactivity towards CO<sub>2</sub> and H<sub>2</sub> not seen for bulk zirconia. C 1 s AP-XPS results indicated that CO<sub>2</sub> molecules adsorbed on Zr/ZrO<sub>x</sub>/Au(111) surfaces could undergo partial decomposition on Zr (CO<sub>2, gas</sub> → CO<sub>gas</sub> + O<sub>ads</sub>), or react with oxygen sites from ZrO<em><sub>x</sub></em> to yield carbonates (Zr-CO<sub>3, ads</sub>). After exposing ZrO<sub>2</sub>/Au (111) surfaces to 1:3 mixtures of CO<sub>2</sub>:H<sub>2</sub>, the formation of HCOO, CO<sub>3</sub>, and CH<sub>3</sub>O was detected in AP-XP spectra. These chemical species decomposed at temperatures in the range of 400‒600 K, making them possible reaction intermediates for methanol synthesis.</p></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":null,"pages":null},"PeriodicalIF":2.1000,"publicationDate":"2024-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Understanding the morphology and chemical activity of model ZrOx/Au (111) catalysts for CO2 hydrogenation\",\"authors\":\"\",\"doi\":\"10.1016/j.susc.2024.122590\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In this study, the growth of ZrO<sub>x</sub> on Au (111) was investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Nanostructures of ZrO<sub>x</sub> (<em>x</em> = 1,2) at the sub-monolayer (≤ 0.3 ML) level were prepared by vapor depositing Zr metal onto Au (111) followed by oxidation with O<sub>2</sub> or CO<sub>2</sub>. At low coverages of the admetal (< 0.05 ML), the formed ZrO<sub>x</sub> nanostructures were dispersed randomly on the terraces and steps of the Au(111) substrate. Strong oxide-metal interactions prevented the formation of islands of zirconia. The ZrO<sub>x</sub> nanostructures displayed a reactivity towards CO<sub>2</sub> and H<sub>2</sub> not seen for bulk zirconia. C 1 s AP-XPS results indicated that CO<sub>2</sub> molecules adsorbed on Zr/ZrO<sub>x</sub>/Au(111) surfaces could undergo partial decomposition on Zr (CO<sub>2, gas</sub> → CO<sub>gas</sub> + O<sub>ads</sub>), or react with oxygen sites from ZrO<em><sub>x</sub></em> to yield carbonates (Zr-CO<sub>3, ads</sub>). After exposing ZrO<sub>2</sub>/Au (111) surfaces to 1:3 mixtures of CO<sub>2</sub>:H<sub>2</sub>, the formation of HCOO, CO<sub>3</sub>, and CH<sub>3</sub>O was detected in AP-XP spectra. These chemical species decomposed at temperatures in the range of 400‒600 K, making them possible reaction intermediates for methanol synthesis.</p></div>\",\"PeriodicalId\":22100,\"journal\":{\"name\":\"Surface Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2024-08-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Surface Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0039602824001419\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Surface Science","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0039602824001419","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
本研究利用扫描隧道显微镜(STM)和同步辐射环境压力 X 射线光电子能谱(AP-XPS)研究了氧化锆在金(111)上的生长。通过在金(111)上气相沉积 Zr 金属,然后用 O2 或 CO2 氧化,制备了亚单层(≤ 0.3 ML)级别的 ZrOx(x = 1,2)纳米结构。在金属覆盖率较低(0.05 ML)的情况下,形成的氧化锆纳米结构随机分散在金(111)基底的台阶和阶梯上。强烈的氧化物-金属相互作用阻止了氧化锆岛的形成。氧化锆纳米结构对 CO2 和 H2 的反应活性是块状氧化锆所不具备的。C 1 s AP-XPS 结果表明,Zr/ZrOx/Au(111)表面吸附的二氧化碳分子可在 Zr 上发生部分分解(CO2,气体 → COgas + Oads),或与 ZrOx 的氧位点反应生成碳酸盐(Zr-CO3,吸附)。将 ZrO2/Au (111) 表面暴露于 1:3 的 CO2:H2 混合物后,在 AP-XP 光谱中检测到 HCOO、CO3 和 CH3O 的形成。这些化学物质在 400-600 K 的温度范围内分解,因此可能是合成甲醇的反应中间体。
Understanding the morphology and chemical activity of model ZrOx/Au (111) catalysts for CO2 hydrogenation
In this study, the growth of ZrOx on Au (111) was investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Nanostructures of ZrOx (x = 1,2) at the sub-monolayer (≤ 0.3 ML) level were prepared by vapor depositing Zr metal onto Au (111) followed by oxidation with O2 or CO2. At low coverages of the admetal (< 0.05 ML), the formed ZrOx nanostructures were dispersed randomly on the terraces and steps of the Au(111) substrate. Strong oxide-metal interactions prevented the formation of islands of zirconia. The ZrOx nanostructures displayed a reactivity towards CO2 and H2 not seen for bulk zirconia. C 1 s AP-XPS results indicated that CO2 molecules adsorbed on Zr/ZrOx/Au(111) surfaces could undergo partial decomposition on Zr (CO2, gas → COgas + Oads), or react with oxygen sites from ZrOx to yield carbonates (Zr-CO3, ads). After exposing ZrO2/Au (111) surfaces to 1:3 mixtures of CO2:H2, the formation of HCOO, CO3, and CH3O was detected in AP-XP spectra. These chemical species decomposed at temperatures in the range of 400‒600 K, making them possible reaction intermediates for methanol synthesis.
期刊介绍:
Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to:
• model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions
• nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena
• reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization
• phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization
• surface reactivity for environmental protection and pollution remediation
• interactions at surfaces of soft matter, including polymers and biomaterials.
Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.