Benedet Mattia, Gallo Andrea, Maccato Chiara, Rizzi Gian Andrea, Barreca Davide, Lebedev Oleg I, Modin Evgeny, McGlynn Ruairi, Mariotti Davide, Gasparotto Alberto
Department of Chemical Sciences, Padova University and INSTM, 35131 Padova, Italy.
CNR-ICMATE and INSTM, Department of Chemical Sciences, Padova University, 35131 Padova, Italy.
ACS Appl Mater Interfaces. 2023 Oct 11;15(40):47368-47380. doi: 10.1021/acsami.3c09363. Epub 2023 Sep 28.
The design and fabrication of eco-friendly and cost-effective (photo)electrocatalysts for the oxygen evolution reaction (OER) is a key research goal for a proper management of water splitting to address the global energy crisis. In this work, we focus on the preparation of supported MnO/graphitic carbon nitride (g-CN) OER (photo)electrocatalysts by means of a novel preparation strategy. The proposed route consists of the plasma enhanced-chemical vapor deposition (PE-CVD) of MnO nanoarchitectures on porous Ni scaffolds, the anchoring of controllable g-CN amounts by an amenable electrophoretic deposition (EPD) process, and the ultimate thermal treatment in air. The inherent method versatility and flexibility afforded defective MnO/g-CN nanoarchitectures, featuring a g-CN content and nano-organization tunable as a function of EPD duration and the used carbon nitride precursor. Such a modulation had a direct influence on OER functional performances, which, for the best composite system, corresponded to an overpotential of 430 mV at 10 mA/cm, a Tafel slope of ≈70 mV/dec, and a turnover frequency of 6.52 × 10 s, accompanied by a very good time stability. The present outcomes, comparing favorably with previous results on analogous systems, were rationalized on the basis of the formation of type-II MnO/g-CN heterojunctions, and yield valuable insights into this class of green (photo)electrocatalysts for end uses in solar-to-fuel conversion and water treatment.
设计和制造用于析氧反应(OER)的环保且经济高效的(光)电催化剂,是合理管理水分解以应对全球能源危机的关键研究目标。在这项工作中,我们专注于通过一种新颖的制备策略来制备负载型MnO/石墨相氮化碳(g-CN)OER(光)电催化剂。所提出的路线包括在多孔镍支架上通过等离子体增强化学气相沉积(PE-CVD)制备MnO纳米结构,通过可控的电泳沉积(EPD)过程锚定可控量的g-CN,以及最终在空气中进行热处理。这种固有的方法通用性和灵活性产生了有缺陷的MnO/g-CN纳米结构,其g-CN含量和纳米组织可根据EPD持续时间和所使用的氮化碳前驱体进行调节。这种调节对OER功能性能有直接影响,对于最佳复合体系,在10 mA/cm²时过电位为430 mV,塔菲尔斜率约为70 mV/dec,周转频率为6.52×10⁻³ s⁻¹,同时具有非常好的时间稳定性。与先前在类似体系上的结果相比,目前的结果基于II型MnO/g-CN异质结的形成得到了合理的解释,并为这类用于太阳能到燃料转化和水处理最终用途的绿色(光)电催化剂提供了有价值的见解。