铁系双金属羟基氧化物的晶相、组成调控及其析氧性能研究

Oxygen evolution reaction (OER) is a bottleneck of the exploitation and utilization of some clean energy, due to its high energy consumption and low efficiency. Based on the OER mechanism of ferro-serial metal compounds, this project intends to design and synthesize the supported ferro-serial bimetallic oxyhydroxides, and study their OER properties. Using the metal-organic complexes as slow-releasing sources, ferro-serial bimetallic oxyhydroxides on the various current collectors (such as graphitic carbon, carbon fiber paper etc.) are proposed to prepare via in-situ growth or later load strategy, utilizing the induced assembly and orientation growth effect. The component, crystalline phase, and the interface characteristics between bimetallic oxyhydroxides and current collectors will be adjusted by experiment parameter, and then, establishing the best balance relationship between the catalytic activity and stability based on the study of OER performance and reaction process in detail. Combined with the theoretical calculation and experimental characterization, an in-depth understanding of the correlations between synthesis, structure and property will be achieved, which hence reveal the influence of the component interactions among the material, lattice distortion, the interface characteristics on the OER property, and disclose the adsorption-dissociation-desorption process and behavior for various small molecules or radicals (such as, OH- and H2O) on the surface of bimetallic oxyhydroxides, as well as the transition state, thermodynamics and kinetics of catalytic nature during OER process. It may afford the theoretical and experimental proof for high-efficient OER catalyst.

高能耗、低效率的析氧反应是多种清洁能源开发利用的瓶颈。基于铁系金属化合物的电催化析氧机制，本项目拟开展担载型铁系双金属羟基氧化物的可控合成及析氧性能研究。以金属-有机配合物为金属缓释源，利用诱导组装、取向生长等作用，采用原位生长或后负载策略，在石墨化碳、碳纤维纸等集流体表面构筑铁系双金属羟基氧化物；通过实验参数调变，控制铁系双金属羟基氧化物的晶相、组成及其与集流体间界面特性；在系统考察电催化析氧性能和反应历程的基础上，确立催化剂活性和稳定性之间的最佳平衡点。结合理论模拟计算和XAFS等现代表征手段，对双金属羟基氧化物的合成-结构-性能三者之间的关系形成本质认识，阐明组分间相互作用、晶格畸变、表（界）面结构对其析氧性能的影响规律；揭示催化反应过程中OH-或H2O在催化剂表面的吸附、解离和脱附过程，以及过渡态、热力学和动力学等催化本质，为构筑高效的电催化析氧材料提供实验和理论依据。

高能耗、低效率的析氧反应（OER）是多种清洁能源开发利用的瓶颈。聚焦于OER反应，发展简单易行的策略合成高效的OER催化材料，探究催化剂微观结构与宏观性能的关系，不仅可以深入理解OER反应机制，而且有助于促进二次金属空电池和水分解制氢技术的发展，对实现能量高效储存与转化具有重要的理论和实际意义。本项目以铁系金属为研究对象，针对电催化OER机制和关键指标，重点开展了铁系金属化合物的晶相、组成等结构调控，结合理论模拟计算和XAFS等现代表征手段，对金属（羟基）氧化物的合成-结构-性能三者之间的关系形成本质认识。发展了原位界面导向组装新策略，成功构筑了铁系金属基二维纳米薄片；通过阳离子和阴离子双向调节，实现了催化剂组分、晶格畸变、表（界）面结构的有效调控；通过化学合成和原位电化学重构等过程构建了铁系（双）金属（羟基）氧化物立体膜；结合双金属协同作用和异质阵列优异的定向传输特性促进析氧过程动力学、实现高效的能量转化。同时，课题组还着重研究了杂原子碳缺陷类型、位置和数量对分解水性活性位调变和催化机制的影响；初步探索了Pd、Sn、Bi基材料电催化CO2还原性能和机制。项目执行期间，发表项目资助的SCI研究论文26篇；申请中国发明专利4项，获授权中国发明专利2项；获黑龙江省科学技术奖一等奖1项(技术发明奖)；培养博士生5名、硕士生17名。