Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts.
Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts.
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DOI：
10.1021/acs.jpcc.7b01744
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发表时间：
2017-04-20
期刊：
影响因子：
--
通讯作者：
Kyriakou G
中科院分区：
文献类型：
--
作者：
Taylor MJ;Jiang L;Reichert J;Papageorgiou AC;Beaumont SK;Wilson K;Lee AF;Barth JV;Kyriakou G
糠醛是一种重要的生物衍生平台化学品，其在氢气气氛下的反应性可提供多种化学中间体。在这里，采用程序升温反应光谱法和互补扫描隧道显微镜（STM）来研究 Pt（111）模型催化剂上的糠醛吸附和反应性。糠醛脱羰生成呋喃对反应条件高度敏感，特别是表面拥挤和吸附几何形状的相关变化：糠醛在低覆盖率的清洁 Pt(111) 上采用平面几何形状，在高覆盖率时倾斜，形成致密的糠醛吸附层。吸附几何结构的这种转变强烈影响产物的选择性。 STM 揭示了平面糠醛氢键网络的形成，这有利于干净的 Pt(111) 脱羰和共吸附氢存在下的氢解。预吸附的氢气促进糠醛加氢为糠醇，并随后氢解为甲基呋喃，同时抑制残留的表面碳。 Pt 上的糠醛化学性质与 Pd 上的糠醛化学性质明显不同，前者的吸附较弱，但产物分布比后者更简单；钯催化更广泛的化学反应，包括开环形成丙烯。深入了解分子取向在控制产物选择性中的作用将指导更具选择性和稳定性的糠醛加氢铂催化剂的设计和操作。
Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.
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影响因子：
8.4
作者：
Audemar, Maite;Ciotonea, Carmen;Jerome, Francois
通讯作者：
Jerome, Francois
DOI：
10.1039/b712664f
发表时间：
2009-01-01
期刊：
CATALYSIS, VOL 21
影响因子：
--
作者：
Egeblad, Kresten;Rass-Hansen, Jeppe;Christensen, Claus Hviid
通讯作者：
Christensen, Claus Hviid
影响因子：
3.7
作者：
Goubert, Guillaume;Groves, Michael N.;Hammer, Bjork
通讯作者：
Hammer, Bjork
影响因子：
3.7
作者：
Lawton, T. J.;Pushkarev, V.;Sykes, E. C. H.
通讯作者：
Sykes, E. C. H.
影响因子：
3.7
作者：
Merlo, Andrea B.;Vetere, Virginia;Casella, Monica L.
通讯作者：
Casella, Monica L.