Establishing processing-structure-property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T′ (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG H), and, with respect to catalysis, the 1T′ transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Indeed, we show basal plane activation of 1T′ molybdenum disulfide and a lowering of ΔG H from +1.6 eV for 2H to +0.18 eV for 1T′, comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.
Lithiation-exfoliation produces single to few-layered MoS2 and WS2 sheets dispersible in water. However, the process transforms them from the pristine semiconducting 2H phase to a distorted metallic phase. Recovery of the semiconducting properties typically involves heating of the chemically exfoliated sheets at elevated temperatures. Therefore, it has been largely limited to sheets deposited on solid substrates. We report the dispersion of chemically exfoliated MoS2 sheets in high boiling point organic solvents enabled by surface functionalization and the controllable recovery of their semiconducting properties directly in solution. Ultimately, this process connects the scalability of chemical exfoliation with the simplicity of solution processing, enabling a facile method for tuning the metal to semiconductor transitions of MoS2 and WS2 within a liquid medium.
This is the final report for the President Harry S. Truman Fellowship in National Security Science and Engineering (LDRD project 130813) awarded to Dr. Bryan Kaehr from 2008-2011. Biological chemistries, cells, and integrated systems (e.g., organisms, ecologies, etc.) offer important lessons for the design of synthetic strategies and materials. The desire to both understand and ultimately improve upon biological processes has been a driving force for considerable scientific efforts worldwide. However, to impart the useful properties of biological systems into modern devices and materials requires new ideas and technologies. The research herein addresses aspects of these issues through the development of (1) a rapid-prototyping methodology to build 3D bio-interfaces and catalytic architectures, (2) a quantitative method to measure cell/material mechanical interactions in situ and at the microscale, and (3) a breakthrough approach to generate functional biocomposites from bacteria and cultured cells.