Cerium oxide (ceria) plays an important and fascinating role in heterogeneous catalysis as illustrated by its versatile use as a catalyst, a catalyst support, or a promotor in various oxidation and reduction reactions. Central to these reactions is the rich defect chemistry, facile redox capability, and unusual acid-base properties of ceria. Understanding the unique redox and acid-base properties of ceria is essential to build the structure-catalysis relationship so that improved catalytic functions can be achieved for ceria-based materials. Among the characterization toolbox, spectroscopic approach indisputably stands out for its unparalleled power in offering chemical insights into the surface properties of ceria at atomic and molecular level. In this review, we summarize advances in revealing the redox and acid-base properties of ceria via a variety of spectroscopic methods including optical, X-ray, neutron, electronic and nuclear spectroscopy. Both direct spectroscopy characterization and its coupling with probe molecules are analyzed to illustrate how the nature, strength and density of different surface sites are influenced by the pretreatment, the morphology and size of ceria nanoparticles. Further directions in taking advantage of in situ/operando spectroscopy for better understanding the catalysis of ceria-based materials are proposed in the summary and outlook section.

氧化铈（二氧化铈）在多相催化中扮演着重要而迷人的角色，这体现在它在各种氧化和还原反应中作为催化剂、催化剂载体或促进剂的多功能用途。这些反应的核心是氧化铈丰富的缺陷化学性质、易氧化的氧化还原能力和不寻常的酸碱特性。了解氧化铈独特的氧化还原和酸碱性质对于建立结构-催化关系至关重要，以便可以实现基于氧化铈的材料的改进催化功能。在表征工具箱中，光谱方法无可争议地以其无与伦比的能力脱颖而出，在原子和分子水平上提供对氧化铈表面特性的化学洞察力。在这次审查中，我们总结了通过各种光谱方法（包括光学、X 射线、中子、电子和核光谱）揭示氧化还原和酸碱特性的进展。分析了直接光谱表征及其与探针分子的耦合，以说明不同表面位点的性质、强度和密度如何受到预处理、氧化铈纳米颗粒的形态和尺寸的影响。利用的进一步方向摘要和展望部分提出了原位/操作光谱，以更好地了解基于氧化铈的材料的催化作用。