Wen-jing Yao, Sheng Liao, Hao-yi Fu, Wen-yi Xu, Meng Xu, Dan Zhao* and Chao Chen,
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The catalytic performance of samples was comprehensively analyzed by the HPLC technique, <sup>1</sup>H NMR spectra, and various electrochemical tests, indicating that the introduction of DyPO<sub>4</sub> in a proper amount (<i>m</i> = 0.16) would significantly enhance the catalytic efficiency versus singular Ni<sub>2</sub>P in terms of 2,5-FDCA yield (91 vs 26%), selectivity (99 vs 47%), and Faradaic Efficiency (F.E.: 98 vs 70%). The enhancements were accompanied by improved kinetic features such as the Tafel slope (53 vs 95 mV dec<sup>–1</sup>) and intrinsic activity (3.3 vs 1.7 mA cm<sup>–2</sup>). The boosting endowment (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P stands among the top members of reported Ni-based HMFOR catalysts. The promoter effect of DyPO<sub>4</sub> was further investigated by H<sub>2</sub>O-TPD, contact angle, zeta potential, OCP, and EIS measurements. It was testified that the nonhydrophilic Ni<sub>2</sub>P surface would be converted to a hydrophilic composite interface with the introduction of DyPO<sub>4</sub>; in line with the essential change, transfer of reactants and activation of water were obviously intensified with the lowered charge transfer resistance along the catalytic interface, which was responsible for the enhanced catalytic behavior of (DyPO<sub>4</sub>)<sub><i>m</i></sub>/Ni<sub>2</sub>P versus Ni<sub>2</sub>P. 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引用次数: 0
摘要
虽然许多绿色和可持续的催化转化都涉及到水,但催化界面的亲水性却很少得到特别的关注。针对这一问题,本文制备了用于5-羟甲基糠醛氧化反应(HMFOR)生成2,5-呋喃二羧酸(2,5- fdca)的Dy-Ni-P催化剂。通过ICP-OES、XRD、XPS和HRTEM表征,证实催化剂为(DyPO4)m/Ni2P复合材料,摩尔比m在0.08 ~ 0.28之间。通过HPLC技术、1H NMR谱和各种电化学测试对样品的催化性能进行综合分析,结果表明,与单一Ni2P相比,引入适量的DyPO4 (m = 0.16)在2,5- fdca产率(91 vs 26%)、选择性(99 vs 47%)和法拉第效率(F.E: 98 vs 70%)方面显著提高了催化效率。这种增强还伴随着动力学特性的改善,如塔菲尔斜率(53 vs 95 mV dec1)和固有活性(3.3 vs 1.7 mA cm-2)。助推禀赋(DyPO4)m/Ni2P是已报道的ni基HMFOR催化剂中的顶级成员。通过H2O-TPD、接触角、zeta电位、OCP和EIS测量进一步研究了DyPO4的促进剂效应。结果表明,引入DyPO4后,非亲水Ni2P表面转变为亲水复合界面;与本质变化一致的是,随着(DyPO4)m/Ni2P在催化界面上电荷转移阻力的降低,反应物的转移和水的活化明显加强,这是(DyPO4)m/Ni2P相对于Ni2P催化性能增强的原因。上述发现使得关于水的话题表明,催化界面的亲水性在促进涉及水的多相催化转化中起着重要作用;以目前HMFOR的(DyPO4)m/Ni2P为例,稀土磷酸盐可以被认为是一种优秀的亲水性促进剂,可以为涉及水的重要化学工程创新优秀的催化剂。
Impact of Rare-Earth Phosphate as a Hydrophilic Promoter on Boosting Electrooxidation of 5-Hydroxymethylfurfural: A DyPO4/Ni2P Example
The hydrophilic property of the catalytic interface has been seldom focused on particularly, although many green and sustainable catalysis transformations involve water. Addressing the issue, we prepared Dy–Ni–P catalysts for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) to 2,5-furandicarboxylic acid (2,5-FDCA) in this work. The catalysts were clarified as (DyPO4)m/Ni2P composites with molar ratio m within 0.08–0.28 by ICP-OES, XRD, XPS, and HRTEM characterizations. The catalytic performance of samples was comprehensively analyzed by the HPLC technique, 1H NMR spectra, and various electrochemical tests, indicating that the introduction of DyPO4 in a proper amount (m = 0.16) would significantly enhance the catalytic efficiency versus singular Ni2P in terms of 2,5-FDCA yield (91 vs 26%), selectivity (99 vs 47%), and Faradaic Efficiency (F.E.: 98 vs 70%). The enhancements were accompanied by improved kinetic features such as the Tafel slope (53 vs 95 mV dec–1) and intrinsic activity (3.3 vs 1.7 mA cm–2). The boosting endowment (DyPO4)m/Ni2P stands among the top members of reported Ni-based HMFOR catalysts. The promoter effect of DyPO4 was further investigated by H2O-TPD, contact angle, zeta potential, OCP, and EIS measurements. It was testified that the nonhydrophilic Ni2P surface would be converted to a hydrophilic composite interface with the introduction of DyPO4; in line with the essential change, transfer of reactants and activation of water were obviously intensified with the lowered charge transfer resistance along the catalytic interface, which was responsible for the enhanced catalytic behavior of (DyPO4)m/Ni2P versus Ni2P. The above discovery made the topic regarding water indicate that the hydrophilic property of the catalytic interface played a significant role in facilitating heterogeneous catalysis transformations involving water; exampled by the current (DyPO4)m/Ni2P for HMFOR, rare-earth phosphate could be referred to as an outstanding hydrophilic promoter to innovate excellent catalysts for technology-important chemical engineering involving water.
期刊介绍:
ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.