Gaining Molecular Insights into Porous Niobium-based Catalysts for One-pot Biomass Upgrading

获得用于一锅生物质升级的多孔铌基催化剂的分子洞察

• 批准号: EP/P011632/1
• 负责人: Sihai Yang
• 金额: $ 12.86万
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2017
• 资助国家: 英国
• 起止时间: 2017 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FP011632%2F1
• 关键词: Gaining; Molecular; Insights; into; Porous

As a sustainable source of organic carbon, biomass is playing an increasingly important role in our energy landscape. Lignocellulose, as the main component of woody biomass, is composed of cellulose, hemicellulose, and lignin. The upgrading of renewable lignocellulosic biomass is particularly attractive to bridge future gaps in the supply of chemical fuels and feedstocks. However, due to the complexity of the molecular structure of lignocellulosic biomass, particularly for the lignin portion, and its notorious resistance to chemical transformation, energy-efficient and cost-effective production of liquid fuels and chemical feedstocks from lignocellulose remains a highly challenging task worldwide. Recently, a family of porous Nb-based catalysts (Ru, Pt or Pd loaded porous NbOPO4 or Nb2O5) have exhibited an outstanding performance for the conversion of lignocellulosic biomass (190 oC, 5 MPa H2, 20 h) and bulk lignin (250 oC, 0.5 MPa H2, 20 h) into alkanes and arenes, respectively, via one-pot reactions. These reactions enable the complete removal of oxygen from biomass to produce liquid hydrocarbons and avoid chemical pre-treatment to the raw biomass materials, thus leading to potential energy savings in the biomass refinery based upon these novel catalysts. However, to date, little information on the catalytic active site or mechanism is known for these systems and little effort has been devoted to investigating the structural changes of these catalysts upon cycling reactions, where decreased activity/selectivity was often seen. Gaining in-depth understanding on the reaction mechanism and catalysts stability is of fundamental importance for the development of improved catalytic systems. This proposal will systematically investigate the binding dynamics, activation and conversion of the substrate molecules on the surface of the catalysts by a combination of spectroscopic, crystallographic and computational approaches. In particular, inelastic neutron scattering, a very powerful but rarely used spectroscopic technique, will be applied extensively to gain molecular details on these catalytic upgrading reactions of renewable biomass for the production of liquid fuels and high value aromatic chemicals. More importantly, the stability and details on structural degradation of the catalysts will be studied in situ under flow conditions via time-resolved X-ray crystallography and a range of chemical analytic approaches. The essential goal of converting biomass (esp. for the cellulose and hemicellulose portion) into liquid hydrocarbon fuels is the complete removal of oxygen through the cleavage of C-O bonds during the one-pot reaction. This project will determine the most stable reaction intermediate/s on the surface of catalysts and the stepwise pathway for the rate-determining steps (esp. for the cleavage of C-O bonds) within the entire conversion. In this way, we will understand the unique feature of these porous Nb-based catalysts in cleaving the C-O bonds to achieve the complete removal of oxygen from the system. The success of this project will not only gain in-depth understanding of the catalytic mechanism for some highly important but challenging biomass upgrading reactions, but also afford key insights into the design of new catalysts with improved structural stability and catalytic activity. This proposal involves multiple collaborations with Central Facilities and will strengthen the links between neutron scattering and catalysis.

作为一种可持续的有机碳来源，生物质在我们的能源格局中发挥着越来越重要的作用。木质纤维素是木本生物质的主要成分，由纤维素、半纤维素和木质素组成。可再生木质纤维素生物质的升级对于弥合化学燃料和原料供应的未来缺口特别有吸引力。然而，由于木质纤维素生物质的分子结构的复杂性，特别是对于木质素部分，以及其对化学转化的众所周知的抗性，从木质纤维素生产液体燃料和化学原料的能量有效和成本有效仍然是世界范围内极具挑战性的任务。近年来，一类多孔铌基催化剂（负载Ru、Pt或Pd的多孔NbOPO 4或Nb 2 O 5）在一锅法将木质纤维素生物质（190 ℃，5 MPa H2，20 h）和本体木质素（250 ℃，0.5 MPa H2，20 h）分别转化为烷烃和芳烃方面表现出了优异的性能。这些反应使得能够从生物质中完全去除氧气以产生液态烃，并且避免对生物质原料进行化学预处理，从而导致基于这些新型催化剂的生物质精炼中的潜在能量节省。然而，迄今为止，很少有关于这些系统的催化活性位点或机理的信息是已知的，并且很少有人致力于研究这些催化剂在循环反应时的结构变化，其中经常看到活性/选择性降低。深入了解反应机理和催化剂的稳定性对改进催化体系具有重要意义。本研究将结合光谱学、晶体学和计算方法，系统地研究底物分子在催化剂表面的结合动力学、活化和转化。特别是，非弹性中子散射，一个非常强大的，但很少使用的光谱技术，将被广泛应用，以获得这些可再生生物质的催化升级反应的分子细节，用于生产液体燃料和高价值的芳香族化学品。更重要的是，将通过时间分辨X射线晶体学和一系列化学分析方法在流动条件下原位研究催化剂的稳定性和结构降解细节。将生物质（特别是纤维素和半纤维素部分）转化为液态烃燃料的基本目标是在一锅反应期间通过C-O键的裂解完全除去氧。该项目将确定催化剂表面上最稳定的反应中间体，以及整个转化过程中速率决定步骤（特别是C-O键断裂）的分步途径。通过这种方式，我们将了解这些多孔Nb基催化剂在裂解C-O键以实现从系统中完全去除氧方面的独特功能。该项目的成功不仅将深入了解一些非常重要但具有挑战性的生物质升级反应的催化机理，而且还将为设计具有改进的结构稳定性和催化活性的新型催化剂提供关键见解。该提案涉及与中央设施的多项合作，并将加强中子散射和催化之间的联系。

项目成果

Selective production of arenes via direct lignin upgrading over a niobium-based catalyst.

通过铌基催化剂直接木质素升级选择性生产芳烃

• DOI: 10.1038/ncomms16104
• 发表时间: 2017-07-24
• 期刊: Nature communications
• 影响因子: 16.6
• 作者: Shao Y;Xia Q;Dong L;Liu X;Han X;Parker SF;Cheng Y;Daemen LL;Ramirez-Cuesta AJ;Yang S;Wang Y
• 通讯作者: Wang Y

Acid-Free Conversion of Cellulose to 5-(Hydroxymethyl)furfural Catalyzed by Hot Seawater

热海水催化纤维素无酸转化为 5-(羟甲基)糠醛

• DOI: 10.1021/acs.iecr.8b00443
• 发表时间: 2018-02
• 期刊: Industrial & Engineering Chemistry Research
• 影响因子: 4.2
• 作者: Li Xiangcheng;Zhang Yayun;Xia Qineng;Liu Xiaohui;Peng Kaihao;Yang Sihai;Wang Yanqin
• 通讯作者: Wang Yanqin

Breaking the Limit of Lignin Monomer Production via Cleavage of Interunit Carbon-Carbon Linkages

通过单元间碳-碳键的断裂突破木质素单体生产的极限

• DOI: 10.1016/j.chempr.2019.03.007
• 发表时间: 2019-06-13
• 期刊: CHEM
• 影响因子: 23.5
• 作者: Dong, Lin;Lin, Longfei;Wang, Yanqin
• 通讯作者: Wang, Yanqin

Control of zeolite microenvironment for propene synthesis from methanol.

• DOI: 10.1038/s41467-021-21062-1
• 发表时间: 2021-02-05
• 期刊: Nature communications
• 影响因子: 16.6
• 作者: Lin L;Fan M;Sheveleva AM;Han X;Tang Z;Carter JH;da Silva I;Parlett CMA;Tuna F;McInnes EJL;Sastre G;Rudić S;Cavaye H;Parker SF;Cheng Y;Daemen LL;Ramirez-Cuesta AJ;Attfield MP;Liu Y;Tang CC;Han B;Yang S
• 通讯作者: Yang S

Investigations of Hydrocarbon Species on Solid Catalysts by Inelastic Neutron Scattering

• DOI: 10.1007/s11244-020-01389-7
• 发表时间: 2020-10
• 期刊: Topics in Catalysis
• 影响因子: 3.6
• 作者: Longfei Lin;Q. Mei;Xue Han;S. Parker;Sihai Yang