Lithium Ion Battery Materials as Tunable, Redox Non-Innocent Catalyst Supports

The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end, herein we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (LixMn2O4) to yield isolated Ni(II) occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/LixMn2O4). The activity of Ni/LixMn2O4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/LixMn2O4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on LixTiO2, demonstrating the generality of this phenomenon.

Application of Ferrites as Electrodes for Supercapacitor

Apart from the magnetic properties, ferrites have been considered as efficient electrodes for next generation energy storage devices. This chapter will include applications of spinel ferrites such as MnFe2O4, CoFe2O4, ZnFe2O4 and NiFe2O4 in supercapacitor. In ferrites, the charge storage arises from the fast-reversible surface redox reactions at the electrode/electrolyte interface. In particular, the electrode material with high specific capacitance, wide range of operating potential, low synthesis cost and its availability on the earth are highly desirable to fabricate a supercapacitor. Ferrites with mixed oxidation states have proved as promising electrodes in supercapacitors. In this chapter, we summarize the different synthesis methods of ferrites based nanocomposites and their electrochemical properties for supercapacitor application.

Mineral protection regulates the long-term global preservation of natural organic carbon

<p>The vast majority of organic carbon (OC) produced by life is respired back to carbon dioxide (CO<sub>2</sub>), but roughly 0.1% escapes and is preserved over geologic timescales. By sequestering reduced carbon from Earth’s surface, this “slow OC leak” contributes to CO<sub>2</sub> removal and promotes the accumulation of atmospheric oxygen and oxidized minerals. Countering this, OC contained within sedimentary rocks is oxidized during exhumation and erosion of mountain ranges. By respiring previously sequestered reduced carbon, erosion consumes atmospheric oxygen and produces CO<sub>2</sub>. The balance between these two processes—preservation and respiration—regulates atmospheric composition, Earth-surface redox state, and global climate. Despite this importance, the governing mechanisms remain poorly constrained. To provide new insight, we developed a method that investigates OC composition using bond-strength distributions coupled with radiocarbon ages. Here I highlight a suite of recent results using this approach, and I show that biospheric OC interacts with particles and becomes physiochemically protected during aging, thus promoting preservation. I will discuss how this mechanistic framework can help elucidate why OC preservation—and thus atmospheric composition, Earth-surface redox state, and climate—has varied throughout Earth history.</p>

MOF-based photocatalysts for hydrogen production

: Metal-Organic Frameworks (MOFs) are a class of porous crystalline materials that assembled by multiple metal ions and organic linkers, featuring with high specific surface area and tailorable structures. MOFs exhibit semiconductorlike behavior due to the inorganic fragment in the framework. Principally, the perfect crystalline structure inhibit the formation of charge recombination centers, and their porous characters facilitate the rapid/efficient utilization of the photogenerated electrons and holes. Therefore, in recent years, MOF based materials have received increasing attention for application in photocatalysis. Here, starting from the photocatalytic mechanism toward hydrogen production on MOF based materials, the three key photocatalytic processes: light absorption, electron-hole separation and surface redox reactions, will be illustrated according to the recent reports. In addition, MOF derivatives for photocatalytic hydrogen production is briefly introduced. Finally, the conclusions and perspectives are provided to in-depth elucidate the future development of MOF based photocatalysts.

A persistently low level of atmospheric oxygen in Earth’s middle age

Resolving how Earth surface redox conditions evolved through the Proterozoic Eon is fundamental to understanding how biogeochemical cycles have changed through time. The redox sensitivity of cerium relative to other rare earth elements and its uptake in carbonate minerals make the Ce anomaly (Ce/Ce*) a particularly useful proxy for capturing redox conditions in the local marine environment. Here, we report Ce/Ce* data in marine carbonate rocks through 3.5 billion years of Earth’s history, focusing in particular on the mid-Proterozoic Eon (i.e., 1.8 – 0.8 Ga). To better understand the role of atmospheric oxygenation, we use Ce/Ce* data to estimate the partial pressure of atmospheric oxygen (pO2) through this time. Our thermodynamics-based modeling supports a major rise in atmospheric oxygen level in the aftermath of the Great Oxidation Event (~ 2.4 Ga), followed by invariant pO2 of about 1% of present atmospheric level through most of the Proterozoic Eon (2.4 to 0.65 Ga).