Surface hydroxyl group dominating aerobic oxidation of methane below room temperature†

IF 32.4 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Energy & Environmental Science Pub Date : 2024-09-18 DOI:10.1039/D4EE03508A
Baiyang Yu, Lu Cheng, Jiaju Wu, Bing Yang, Hong Li, Jing Xu, Ying Zhang, Chengsi Pan, Xiao-Ming Cao, Yongfa Zhu and Yang Lou
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Abstract

Direct oxidation of methane (DOM) using molecular oxygen (O2) and hydrogen (H2) is currently considered to be triggered by in situ produced H2O2 or free hydroxyl radicals (˙OH). However, the role of the surface hydroxyl group in the DOM that is in situ formed from O2 and H2 has long been ignored. Herein, we provide experimental evidence that DOM using H2 and O2 over titanium silicate-supported single Pd atoms coated with an ultrathin N-doped carbon (Pd1/TS-1@CN) catalyst is dominated by a surface hydroxyl group instead of H2O2 or free ˙OH. Furthermore, the direct bonding between Pd atoms with the pyrrolic nitrogen of the coating layers reinforces the bonding strength of Pd1 and framework oxygen, forming a unique N1–Pd1–O2 configuration that considerably boosts the stability of isolated Pd active sites and their capability to stably generate a surface hydroxyl group from H2 and O2. Therefore, Pd1/TS-1@CN yields a liquid oxygenate productivity of 647 μmol gcat−1 h−1 with 100% selectivity at 15 °C and high stability over 30 cycles with no activity loss. Our findings regarding the catalytic role of the surface hydroxyl group in DOM and its stabilization strategy open up a new avenue for designing advanced catalysts for the DOM using O2 under mild reaction conditions.

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表面羟基主导室温以下甲烷的有氧氧化作用†.
使用分子氧(O2)和氢(H2)直接氧化甲烷(DOM)目前被认为是由原位产生的 H2O2 或游离羟基自由基(-OH)引发的。然而,由 O2 和 H2 在原位形成的 DOM 中表面羟基的作用长期以来一直被忽视。在此,我们提供了实验证据,证明在硅酸钛支撑的单钯原子包覆超薄掺杂 N 的碳(Pd1/TS-1@CN)催化剂上使用 H2 和 O2 生成的 DOM 是由表面羟基而不是 H2O2 或游离 -OH 主导的。此外,Pd 原子与涂层层吡咯烷酮氮之间的直接键合加强了 Pd1 与框架氧的键合强度,形成了独特的 N1-Pd1-O2 构型,大大提高了孤立 Pd 活性位点的稳定性及其从 H2 和 O2 稳定生成表面羟基的能力。因此,Pd1/TS-1@CN 在 15 °C 时可产生 647 μmol-gcat-1-h-1 的液态含氧化合物,具有 100% 的选择性,并且在 30 个循环中保持高度稳定性,活性没有降低。我们关于 DOM 表面羟基的催化作用及其稳定策略的发现,为在温和的反应条件下利用 O2 设计先进的 DOM 催化剂开辟了一条新途径。
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来源期刊
Energy & Environmental Science
Energy & Environmental Science 化学-工程:化工
CiteScore
50.50
自引率
2.20%
发文量
349
审稿时长
2.2 months
期刊介绍: Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences." Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).
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