Very Low Field 2.35 T Solid State NMR Console and Fast MAS NMR Probe for the Study of Paramagnetic Materials Systems

用于研究顺磁性材料系统的极低场 2.35 T 固态 NMR 控制台和快速 MAS NMR 探头

• 批准号: EP/K024418/1
• 负责人: John Hanna
• 金额: $ 8.28万
• 依托单位: University of Warwick
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2013
• 资助国家: 英国
• 起止时间: 2013 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FK024418%2F1
• 关键词: Very; Low; Field; 2.35; Solid

The aim of this proposal is to expand the capability base that solid state NMR community has at its disposal so that more materials and chemistry systems can be effectively studied with this technique. Solid state NMR usually confines itself to the study of diamagnetic materials and compounds; i.e. systems that do not possess unpaired electrons in their electronic structure. Many modern materials and chemical systems being developed possess transition metals and/or rare earth species as part of the elemental composition; these introduce unpaired electrons into these systems and thus promote paramagnetic characteristics which are incompatible with the conventional NMR methodology. Our traditional mindset of how we approach the typical NMR measurement needs to be adjusted as our typical drive to higher external magnetic field strengths is counterproductive in this case. The electron polarisation that gives rise to paramagnetic anisotropies and shifts scales linearly with magnetic field, and these effects greatly detract from conventional NMR data thus masking the information that is normally sought. Severe cases of paramagnetism can preclude the NMR measurement of some systems completely.The most direct way to address this solid state NMR challenge is to attempt measurements in a much reduced (rather than increased) magnetic field, and to spin the sample at very high MAS frequencies. This low field/fast MAS methodology maximises the chance for NMR data to be elucidated from these systems, however these types of NMR spectrometers are very rare commodities worldwide. While many thousand NMR instruments exist throughout the world at fields of 7.05 T (300 MHz for 1H) and above, only a handful of operational low field spectrometers exist to undertake these type of measurements; furthermore, the UK is not well catered for in this field of spectroscopy apart from very limited proof-of-concept pilot studies that have demonstrated this idea. This new capability will be as easy to operate as conventional solid state NMR instrumentation and no specific additional training is required to enable its usage for data acquisition. The impact of this methodology is expected to influence the fields of catalysis and energy materials (battery materials, solid oxide and H conduction fuel cells, hydrogen storage materials, supported metal nanoparticles systems, zeolites, nuclear waste glasses etc.), general organometallc and inorganic chemistry, and the emerging field of medical engineering (rare earth doped biomaterials for oncology and blood vessel growth stimulation applications). It is also expected that this methodology will bridge across to established techniques such as EPR, and emerging technologies such as DNP, both of which employ different strategies for the manipulation of the paramagnetic interaction. These relationships are expected to stimulate a more vibrant magnetic resonance community that will be capable of collaboratively tackling the challenging research issues that confront the UK. Academic collaborators at Cambridge, Birmingham, Imperial, Queen Mary, Kent, UCL and Lancaster, and industrial partners such as Johnson Matthey and Unilever are all acutely aware of these new solid state NMR possibilities and flexibility that this methodology offers, and they eagerly await the improvements to the measurement technology that a low field/fast MAS combination can offer.The specific objectives that shape this proposal are:(a) to deliver a shared low-field/fast MAS solid state NMR resource to the UK magnetic resonance community that will augment the current UK suite of solid state NMR instrumentation in existence,(b) to put in place a state-of-the-art solid state NMR console and appropriate fast MAS probe technology capable of delivering the most modern experiments,(c) to align this methodology with established characterisation technologies such as EPR and emerging experimental initiatives such as DNP.

该提案的目的是扩大固态NMR社区的能力基础，以便使用该技术有效地研究更多的材料和化学系统。固态NMR通常局限于研究抗磁性材料和化合物;即在其电子结构中不具有不成对电子的系统。许多正在开发的现代材料和化学体系都含有过渡金属和/或稀土物质作为元素组成的一部分;这些物质将不成对电子引入这些体系中，从而促进与常规NMR方法不相容的顺磁特性。我们如何处理典型的NMR测量的传统思维需要调整，因为我们对更高外部磁场强度的典型驱动在这种情况下会适得其反。产生顺磁各向异性和位移的电子极化与磁场成线性比例，这些效应极大地减损了常规NMR数据，从而掩盖了通常寻求的信息。解决这一固态NMR难题的最直接方法是尝试在大大降低（而不是增加）的磁场中进行测量，并在非常高的MAS频率下旋转样品。这种低场/快速MAS方法最大限度地提高了从这些系统中解析NMR数据的机会，但是这些类型的NMR光谱仪在世界范围内非常罕见。虽然全世界有数千台核磁共振仪器在7.05 T（1H为300 MHz）及以上的磁场，但只有少数几台低场光谱仪可以进行这些类型的测量;此外，除了非常有限的概念验证试点研究之外，英国在光谱学领域没有得到很好的满足。这种新功能将像传统的固态NMR仪器一样易于操作，并且不需要特殊的额外培训就可以将其用于数据采集。这种方法的影响预计将影响催化和能源材料领域（电池材料、固体氧化物和H传导燃料电池、储氢材料、负载金属纳米颗粒系统、沸石、核废料玻璃等），一般有机金属和无机化学，以及新兴的医学工程领域（用于肿瘤学和血管生长刺激应用的稀土掺杂生物材料）。还预计，这种方法将跨越既定的技术，如EPR，和新兴的技术，如DNP，这两个采用不同的策略来操纵的顺磁相互作用。这些关系预计将刺激一个更有活力的磁共振社区，将能够合作解决英国面临的具有挑战性的研究问题。剑桥、伯明翰、帝国、玛丽皇后、肯特、伦敦大学学院和兰开斯特的学术合作者，以及约翰逊万丰和联合利华等工业合作伙伴，都敏锐地意识到这种方法所提供的这些新的固态NMR可能性和灵活性，他们热切地期待着低场/快速MAS组合可以提供的测量技术的改进。（a）向英国磁共振界提供共享的低场/快速MAS固态NMR资源，这将增强英国现有的固态NMR仪器套件，（B）安装最先进的固态NMR控制台和能够提供最现代实验的适当的快速MAS探针技术，（c）使这一方法与EPR等已确立的表征技术和DNP等新兴实验举措保持一致。

项目成果

The Impact of Intergrain Phases on the Ionic Conductivity of the LAGP Solid Electrolyte Material Prepared by Spark Plasma Sintering.

• DOI: 10.1021/acsami.3c03839
• 发表时间: 2023-08
• 期刊: ACS applied materials & interfaces
• 影响因子: 9.5
• 作者: Sorina Creţu;David G. Bradley;Liye Feng;O. U. Kudu;L. Nguyen;Tuan‐Tu Nguyen;A. Jamali;J. Chotard;V. Seznec;J. Hanna;Arnaud Demortière;M. Duchamp

Cold sintering of bioglass and bioglass/polymer composites

生物玻璃和生物玻璃/聚合物复合材料的冷烧结

• DOI: 10.1111/jace.19022
• 发表时间: 2023
• 期刊: Journal of the American Ceramic Society
• 影响因子: 3.9
• 作者: Andrews J

In Situ Cross-Linking of Silane Functionalized Reduced Graphene Oxide and Low-Density Polyethylene

• DOI: 10.1021/acsapm.0c00115
• 发表时间: 2020-04
• 期刊: ACS Applied Polymer Materials
• 影响因子: 5
• 作者: S. S. Abbas-S.;Gregory J Rees;G. Patias;C. Dancer;J. Hanna;T. McNally

Crystal Chemistry of Vanadium-Bearing Ellestadite Waste Forms.

• DOI: 10.1021/acs.inorgchem.8b01160
• 发表时间: 2018-07
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Yanan Fang;S. Page;Gregory J Rees;M. Avdeev;J. Hanna;T. White

Cysteamine functionalised reduced graphene oxide modification of maleated poly(propylene)

• DOI: 10.1016/j.polymer.2020.122750
• 发表时间: 2020-08-26
• 期刊: POLYMER
• 影响因子: 4.6
• 作者: Abbas, Syeda S.;Kelly, Nicole L.;McNally, Tony
• 通讯作者: McNally, Tony