Hydrogenolysis of C−O bonds is an important tool for synthesis of valuable fuels and chemicals from biomass. In this contribution, we report that morphologically cross‐shaped HZSM‐5‐loaded Ru nanoparticles have demonstrated high activity in the selective hydrogenolysis of guaiacol to benzene in water with 97 % yield and a rate of 7.8 g g⁻¹ h⁻¹ accompanied with high durability. N₂ sorption analysis showed that Ru/HZSM‐5 (cross‐shaped) had a large mesoporous surface area and pore volume for loading small and uniform Ru nanoparticles, as confirmed by TEM images. The stronger interaction of Ru and cross‐shaped HZSM‐5 was simultaneously confirmed by a higher hydrogen reduction temperature of RuO₂ on calcined Ru/HZSM‐5, a blueshift of Ru^δ+‐(CO)_n, Ru^δ+‐(CO), and Ru⁰‐(CO) species in the IR spectra of adsorbed CO, and a higher Ru 3d_5/2 binding energy in X‐ray photoelectron spectroscopy measurements. The reaction constant in guaiacol hydrogenolysis to phenol over cross‐shaped Ru/HZSM‐5 (0.051 min⁻¹) was 3–4 times higher than that on spherical and cuboid Ru/HZSM‐5 (0.012–0.029 min⁻¹) at identical conditions, attributed to the remarkable hydrogenolysis catalytic capability of Ru nanoparticles on cross‐shaped HZSM‐5. In addition, adsorption of guaiacol and hydrogen was more substantial on cross‐shaped Ru/HZSM‐5, as evidenced by of IR and mass spectroscopy, respectively. The higher adsorption of guaiacol is attributed to the abundant Lewis acid sites on cross‐shaped Ru/HZSM‐5, as the Al−OH enriched Lewis acid sites favor the adsorption of oxygen‐containing guaiacol. The higher rate constant in the primary step, together with the adsorbed high concentrated reactant and hydrogen (with nearly first‐order reaction kinetics) on cross‐shaped Ru/HZSM‐5, facilitates the overall tandem reaction, leading to an excellent hydrogenolysis catalyst working at hydrothermal conditions for biomass conversion.

中文翻译：

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Ru / HZSM-5形态交叉形状催化在水中将愈创木酚串联氢化分解为苯

C-O键的氢解作用是从生物质中合成有价值的燃料和化学物质的重要工具。在此贡献中，我们报告了形态学上呈十字形HZSM-5负载的Ru纳米颗粒在水中将愈创木酚选择性加氢水解为苯的过程中显示出高活性，产率为97％，速率为7.8 g g ^-1  h ^-1并伴有较高的耐用性。N ₂吸附分析表明，Ru / HZSM-5（十字形）具有较大的介孔表面积和孔体积，可装载小的且均匀的Ru纳米颗粒，这已得到TEM图像的证实。同时通过煅烧后的Ru / HZSM-5上RuO ₂的更高的氢还原温度证实了Ru与十字形HZSM-5之间更强的相互作用，这是Ru的蓝移。吸附的CO的IR光谱中的^δ+ -（CO）_n，Ruδ ⁺ -（CO）和Ru ^0-（CO）种类以及X射线光电子能谱测量中较高的Ru 3d _5/2结合能。十字形Ru / HZSM-5上愈创木酚氢解苯酚的反应常数（0.051 min ^-1）比球形和长方体Ru / HZSM-5（0.012-0.029 min ^-1）高3-4倍。）在相同的条件下，归因于Ru纳米颗粒在十字形HZSM-5上的出色的氢解催化能力。此外，十字形Ru / HZSM-5上的愈创木酚和氢的吸附量更大，这分别由红外和质谱证明。愈创木酚的更高吸附归因于十字形Ru / HZSM-5上的大量路易斯酸位，因为富含Al-OH的路易斯酸位有利于含氧愈创木酚的吸附。第一步中较高的速率常数，以及十字形Ru / HZSM-5上吸附的高浓度反应物和氢气（具有接近一级反应动力学），促进了整体串联反应，从而导致出色的氢解催化剂工作在水热条件下进行生物质转化。