Demonstration of Controlled Hydrogen Release Using Rh@GQDs during Hydrolysis of NH3BH3
Demonstration of Controlled Hydrogen Release Using Rh@GQDs during Hydrolysis of NH3BH3
复制标题
NH3BH3 水解过程中使用 Rh@GQD 控制氢释放的演示
DOI：
10.1021/acsami.1c15660
复制
发表时间：
2021-10-15
影响因子：
9.5
通讯作者：
Liu, Xiang
中科院分区：
文献类型：
--
作者：
Chen, Weifeng;Lv, Guo;Liu, Xiang
通过有效的方法实现氢-2的受控释放仍然面临许多挑战。本论文以新型前驱体1，2，4-三羟基苯为原料合成了高质量的石墨烯量子点，并进一步开发了一种多功能的Rh@GQds平台，用于NH3BH3(AB)的可控析氢反应。更重要的是，在H-2演化领域首次引入了多步和无级速度控制的设计概念。通过一种新的设计方案，通过锌离子与乙二胺四乙酸(EDTA)的络合作用，放氢速率可以自由调节并根据需要不断变化。密度泛函理论计算表明，由于锌离子的吸附能(107.98千卡·摩尔~(-1))大于AB的吸附能(36.36千卡·摩尔~(-1))，因此锌离子优先被吸附在Rh(100)上。提出了一种控制机制，即锌离子覆盖纳米催化剂的活性中心以防止析氢，而EDTA可以螯合锌离子以重新激活纳米催化剂以产生氢-2，从而极大地促进了该策略在其他催化反应中的应用。此外，还证明了该协议对不同的储氢材料同样有效。因此，这项工作不仅为H-2的控制生产建立了全新的概念，而且解释了它们的机理，从而显著地促进了H-2能量的利用，对催化的控制过程具有重要的启示作用。
Achieving the controlled release of H-2 through an effective approach still faces many challenges. Herein, high-quality graphene quantum dots (GQDs) are synthesized from a new precursor, 1,2,4-trihydroxy benzene, and a multifunctional platform of Rh@GQDs is further developed for the controlled H-2 evolution upon the hydrolysis of NH3BH3 (AB). More importantly, the designing concepts of multistep and stepless speed controls have been introduced in the domains of both H-2 evolution for the first time. Through a novel designing protocol, the rate of H-2 evolution can be freely regulated and constantly varied on demand by means of chelation between Zn2+ and ethylene diamine tetraacetic acid (EDTA). The density functional theory calculation indicates that Zn2+ has the priority to be adsorbed onto Rh(100) due to its larger adsorption energy (107.98 kcal.mol(-1)) than that of AB (36.36 kcal.mol(-1)). A controlling mechanism is presented such that Zn2+ will cover the active sites of the nanocatalyst to prevent the H-2 evolution, and EDTA can chelate Zn2+ to reactivate the nanocatalyst for the production of H-2, greatly facilitating use of this strategy in other catalytic reactions. Moreover, it is demonstrated that the protocol is equally valid for diverse hydrogen storage materials. Therefore, this work not only establishes whole new concepts for the controlled production of H-2 but also explains their mechanism, thus remarkably advancing the utilization of H-2 energy and significantly enlightening the controlled process of catalysis.