科研成果 by Year: 2016

Microscopic understanding of interaction between H2O and MAPbI3 (CH3NH3PbI3) is essential to further improve efficiency and stability of perovskite solar cells. A complete picture of perovskite from initial physical uptake of water molecules to final chemical transition to its monohydrate MAPbI3·H2O is obtained with in situ infrared spectroscopy, mass monitoring, and X-ray diffraction. Despite strong affinity of MA to water, MAPbI3 absorbs almost no water from ambient air. Water molecules penetrate the perovskite lattice and share the space with MA up to one H2O per MA at high-humidity levels. However, the interaction between MA and H2O through hydrogen bonding is not established until the phase transition to monohydrate where H2O and MA are locked to each other. This lack of interaction in water-infiltrated perovskite is a result of dynamic orientational disorder imposed by tetragonal lattice symmetry. The apparent inertness of H2O along with high stability of perovskite in an ambient environment provides a solid foundation for its long-term application in solar cells and optoelectronic devices.

Methane (CH4 /has a 28-fold greater global warming potential than CO2 over 100 years. Atmospheric CH4 concentration has tripled since 1750. Anthropogenic CH4 emissions from China have been growing rapidly in the past decades and contribute more than 10% of global anthropogenic CH4 emissions with large uncertainties in existing global inventories, generally limited to country-scale statistics. To date, a long-term CH4 emission inventory including the major sources sectors and based on province-level emission factors is still lacking. In this study, we produced a detailed annual bottom-up inventory of anthropogenic CH4 emissions from the eight major source sectors in China for the period 1980-2010. In the past 3 decades, the total CH4 emissions increased from 24.4 [18.6-30.5] TgCH(4) yr(-1) in 1980 (mean [minimum-maximum of 95% confidence interval]) to 44.9 [36.6-56.4] TgCH(4) yr(-1) in 2010. Most of this increase took place in the 2000s decade with averaged yearly emissions of 38.5 [30.6-48.3] TgCH(4) yr(-1). This fast increase of the total CH4 emissions after 2000 is mainly driven by CH4 emissions from coal exploitation. The largest contribution to total CH4 emissions also shifted from rice cultivation in 1980 to coal exploitation in 2010. The total emissions inferred in this work compare well with the EPA inventory but appear to be 36 and 18% lower than the EDGAR4.2 inventory and the estimates using the same method but IPCC default emission factors, respectively. The uncertainty of our inventory is investigated using emission factors collected from state-of-the-art published literatures. We also distributed province-scale emissions into 0.1 degrees x 0.1 degrees maps using socioeconomic activity data. This new inventory could help understanding CH4 budgets at regional scale and guiding CH4 mitigation policies in China.

The photophysics of a series of bichromophoric molecules featuring an intramolecular triplet energy transfer between a triscyclometalated iridium(III) complex and covalently linked organic group are studied. By systematically varying the energy gap (0.1-0.3 eV) between the donor (metal complex) and acceptor (pyrene unit), reversible triplet energy transfer processes with equilibrium constant K ranging from ca. 500 to 40 000 are established. Unique photophysical consequences of such large K values are observed. Because of the highly imbalanced forward and backward energy transfer rates, triplet excitons dominantly populate the acceptor moiety in the steady state, giving rise to ultralong luminescence lifetimes up to 1-4 ms. Because the triscyclometalated Ir and triplet pyrene groups both impart relatively small nonradiative energy loss, decent phosphorescence quantum yields (Phi = 0.1-0.6) are attained in spite of the exceptionally prolonged excited states. By virtue of such precious combination of long-lived triplet state and high Phi, these bichromophoric molecules can serve as highly sensitive luminescent sensors for detecting trace amount of O-2 and as potent photosensitizers for producing singlet oxygen even under low-oxygen content conditions.