Enhancement of short/medium-range order and thermal conductivity in ultrahard sp3 amorphous carbon by C70 precursor.

As an advanced amorphous material, sp3 amorphous carbon exhibits exceptional mechanical, thermal and optical properties, but it cannot be synthesized by using traditional processes such as fast cooling liquid carbon and an efficient strategy to tune its structure and properties is thus lacking. Here we show that the structures and physical properties of sp3 amorphous carbon can be modified by changing the concentration of carbon pentagons and hexagons in the fullerene precursor from the topological transition point of view. A highly transparent, nearly pure sp3-hybridized bulk amorphous carbon, which inherits more hexagonal-diamond structural feature, was synthesized from C70 at high pressure and high temperature. This amorphous carbon shows more hexagonal-diamond-like clusters, stronger short/medium-range structural order, and significantly enhanced thermal conductivity (36.3 ± 2.2 W m-1 K-1) and higher hardness (109.8 ± 5.6 GPa) compared to that synthesized from C60. Our work thus provides a valid strategy to modify the microstructure of amorphous solids for desirable properties.

Brightening Blue Photoluminescence in Nonemission MOF-2 by Pressure Treatment Engineering.

As equally essential as the synthesis of new materials, maneuvering new structure configurations can endow the brand-new functional properties to existing materials, which is also one of the core goals in the synthesis community. In this respect, pressure-induced emission (PIE) that triggers photoluminescence (PL) in nonemission materials is an emerging stimuli-responsive smart materials technology. In the PIE paradigms, harvesting bright PL at ambient conditions, however, has remained elusive. Herein, a remarkable PIE phenomenon is reported in initially nonemission Zn(BDC)(DMF)(H2 O) (MOF-2), which shows bright blue-emission at 455 nm under pressure. Intriguingly, the bright blue PL with an excellent photoluminescence quantum yield up to 70.4% is unprecedentedly retained to ambient conditions upon decompression from 16.2 GPa. The detailed structural analyses combined with density functional theory calculations reveal that hydrogen bonding cooperativity effect elevates powerfully the rotational barrier of the linker rotor to 3.87 eV mol-1 from initial 0.91 eV mol-1 through pressure treatment. The downgrade rotational freedom turns on PL of MOF-2 after releasing pressure completely. This is the first case of harvesting PIE to ambient conditions. These findings offer a new platform for the creation of promising alternatives to high-performance PL materials based on initially nonemission counterparts.

Maximized Green Photoluminescence in Tb-Based Metal-Organic Framework via Pressure-Treated Engineering.

Lanthanide metal-organic frameworks are of great interest in the development of photoluminescence (PL) materials owing to their structural tunability and intrinsic features of lanthanide elements. However, there exists some limitations arising from poor matching with metal ions, thereby exhibiting a weak ligand-to-metal energy transfer (LMET) process. Here we demonstrate a pressure-treated strategy for achieving high PL performance in green-emitting Tb(BTC)(H2 O)6 . The PL quantum yield of pressure-treated sample increased from 50.6 % to 90.4 %. We found that the enhanced hydrogen bonds locked the conjugated configuration formed by two planes of carboxyl group and benzene ring, enabling the promoted intersystem crossing to effectively drive LMET. Moreover, the optimized singlet and triplet states also validated the facilitated LMET process. This work opens the opportunity of structure optimization to improve PL performance in MOFs by pressure-treated engineering.

Ultrahard bulk amorphous carbon from collapsed fullerene.

Amorphous materials inherit short- and medium-range order from the corresponding crystal and thus preserve some of its properties while still exhibiting novel properties1,2. Due to its important applications in technology, amorphous carbon with sp2 or mixed sp2-sp3 hybridization has been explored and prepared3,4, but synthesis of bulk amorphous carbon with sp3 concentration close to 100% remains a challenge. Such materials inherit the short-/medium-range order of diamond and should also inherit its superior properties5. Here, we successfully synthesized millimetre-sized samples-with volumes 103-104 times as large as produced in earlier studies-of transparent, nearly pure sp3 amorphous carbon by heating fullerenes at pressures close to the cage collapse boundary. The material synthesized consists of many randomly oriented clusters with diamond-like short-/medium-range order and possesses the highest hardness (101.9 ± 2.3 GPa), elastic modulus (1,182 ± 40 GPa) and thermal conductivity (26.0 ± 1.3 W m-1 K-1) observed in any known amorphous material. It also exhibits optical bandgaps tunable from 1.85 eV to 2.79 eV. These discoveries contribute to our knowledge about advanced amorphous materials and the synthesis of bulk amorphous materials by high-pressure and high-temperature techniques and may enable new applications for amorphous solids.