Ligand-Bound CO2 as a Nonclassical Route toward Efficient Photocatalytic CO2 Reduction with a Ni N-Confused Porphyrin.

Implementing the synergistic effects between the metal and the ligand has successfully streamlined the energetics for CO2 activation and gained high catalytic activities, establishing the important breakthroughs in photocatalytic CO2 reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N-H group. It is readily deprotonated and exists in an anion form during catalysis. Owing to this functional site, NiNCP gave rise to an outstanding turnover number (TON) as high as 217,000 with a 98% selectivity for CO2 reduction to CO, while the parent Ni(II) porphyrin (NiTPP) was found to be nearly inactive. Our mechanistic analysis revealed a nonclassical reaction pattern where CO2 was effectively activated via the attack of the Lewis-basic ligand. The resulting ligand-bound CO2 adduct could be further reduced to produce CO. This new metal-ligand synergistic effect is anticipated to inspire the design of highly active catalysts for small molecule activations.

Pulse Electrolysis Turns on CO2 Methanation through N-Confused Cupric Porphyrin.

Breaking the D4h symmetry in the square-planar M-N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu-N3 motifs in the N-confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm-2 at >60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X-ray diffraction (XRD), transmission electron microscope (TEM), and in situ X-ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction.

A programmable qudit-based quantum processor.

Controlling and programming quantum devices to process quantum information by the unit of quantum dit, i.e., qudit, provides the possibilities for noise-resilient quantum communications, delicate quantum molecular simulations, and efficient quantum computations, showing great potential to enhance the capabilities of qubit-based quantum technologies. Here, we report a programmable qudit-based quantum processor in silicon-photonic integrated circuits and demonstrate its enhancement of quantum computational parallelism. The processor monolithically integrates all the key functionalities and capabilities of initialisation, manipulation, and measurement of the two quantum quart (ququart) states and multi-value quantum-controlled logic gates with high-level fidelities. By reprogramming the configuration of the processor, we implemented the most basic quantum Fourier transform algorithms, all in quaternary, to benchmark the enhancement of quantum parallelism using qudits, which include generalised Deutsch-Jozsa and Bernstein-Vazirani algorithms, quaternary phase estimation and fast factorization algorithms. The monolithic integration and high programmability have allowed the implementations of more than one million high-fidelity preparations, operations and projections of qudit states in the processor. Our work shows an integrated photonic quantum technology for qudit-based quantum computing with enhanced capacity, accuracy, and efficiency, which could lead to the acceleration of building a large-scale quantum computer.

A generalized multipath delayed-choice experiment on a large-scale quantum nanophotonic chip.

Bohr's complementarity is one central tenet of quantum physics. The paradoxical wave-particle duality of quantum matters and photons has been tested in Young's double-slit (double-path) interferometers. The object exclusively exhibits wave and particle nature, depending measurement apparatus that can be delayed chosen to rule out too-naive interpretations of quantum complementarity. All experiments to date have been implemented in the double-path framework, while it is of fundamental interest to study complementarity in multipath interferometric systems. Here, we demonstrate generalized multipath wave-particle duality in a quantum delayed-choice experiment, implemented by large-scale silicon-integrated multipath interferometers. Single-photon displays sophisticated transitions between wave and particle characters, determined by the choice of quantum-controlled generalized Hadamard operations. We characterise particle-nature by multimode which-path information and wave-nature by multipath coherence of interference, and demonstrate the generalisation of Bohr's multipath duality relation. Our work provides deep insights into multidimensional quantum physics and benchmarks controllability of integrated photonic quantum technology.

Single longitudinal mode GaAs-based quantum dot laser with refractive index perturbation.

We report on the design, fabrication, and characterization of single longitudinal mode InAs/GaAs quantum dot lasers emitting at the 1.3 µm communication band. The influence of simply etched surface high-order gratings in the ridge of the Fabry-Perot lasers has been studied. A 35th-order surface grating is fabricated by standard photolithography to introduce the refractive index perturbation, which leads to the reduced mirror loss at the desired wavelength and thus realizing single longitudinal mode lasing. Stable single-mode operations are maintained at the injection current range of 45-100 mA with a side-mode suppression ratio up to 33 dB.

Ultra-broadband tunable single- and double-mode InAs/InP quantum dot external-cavity laser emitting around 1.65 µm.

We report an ultra-wide tunable single- and double-mode InAs/InP quantum dot (QD) external-cavity (EC) laser in a Littrow configuration. By combining the high modal gain of the QD material in the long wavelength range and an anti-reflection/high-reflection facet coating, the entire single-mode tuning range was increased up to 190 nm under a relatively low constant pulsed injection current. Furthermore, the tunable range was further increased to 230 nm at different bias currents. In addition, a mode spacing as wide as 100 nm was achieved using the same QD-EC device in the dual-mode operation, corresponding to a frequency difference of approximately 11 THz.

Continuously tunable mode-spacing of a dual-mode external cavity InAs/InP quantum dot laser.

A tunable double-mode external cavity InAs/InP quantum dot laser based on a dual-Littrow configuration is demonstrated. A 115 nm single-mode tuning spectrum with obviously varied mode intensity has been obtained. A modified tuning method has been adopted to realize continuously tunable mode-spacing between two modes. It is found that single and double modes coexist in the tuning spectrum when one grating angle is fixed while the other grating is rotated; the biggest mode-spacing between double modes is about 75 nm. A continuously tunable range of mode-spacing between double wavelengths has reached up to 80 nm by inserting an attenuation slice in the external optical feedback paths to balance the intensity of the double modes; the separation of double modes is about 50 nm at best. The average output power of the double-mode laser is about a few milliwatts.

Hydrogen sulfide improves drought tolerance in Arabidopsis thaliana by microRNA expressions.

Hydrogen sulfide (H2S) is a gasotransmitter and plays an important role in many physiological processes in mammals. Studies of its functions in plants are attracting ever growing interest, for example, its ability to enhance drought resistance in Arabidopsis. A general role of microRNAs (miRNAs) in plant adaptive responses to drought stress has thereby increased our interest to delve into the possible interplay between H2S and miRNAs. Our results showed that treating wild type (WT) Arabidopsis seedlings with polyethylene glycol 8000 (PEG8000) to simulate drought stress caused an increase in production rate of endogenous H2S; and a significant transcriptional reformation of relevant miRNAs, which were also triggered by exogenous H2S in WT. When lcd mutants (with lower H2S production rate than WT) were treated with PEG8000, they showed lower levels of miRNA expression changes than WT. In addition, we detected significant changes in target gene expression of those miRNAs and the corresponding phenotypes in lcd, including less roots, retardation of leaf growth and development and greater superoxide dismutase (SOD) activity under drought stress. We thereby conclude that H2S can improve drought resistance through regulating drought associated miRNAs in Arabidopsis.

Surface acylation of cellulose whiskers by drying aqueous emulsion.

A simple chemical modification route to confer high hydrophobicity to crystalline cellulose surface was demonstrated using tunicin whiskers as model material. An alkyenyl succinic anhydride (ASA) aqueous emulsion was mixed with cellulose suspension, freeze-dried, and heated to 105 degrees C. The bulk degree of substitution (DS) was evaluated by FT-IR spectrometry, elemental analysis, and weight gain. The surface DS was quantified by X-ray photoelectron spectroscopy. The surface-acylated whiskers retained their morphological and crystalline integrity, but due to their surface acylation, they are readily dispersible in solvents of low polarity such as 1,4-dioxane. These whiskers can also be well dispersed in polystyrene to form a nanocomposite.