Electrospun Cellulose Nanocrystals Reinforced Flexible Sensing Paper for Triboelectric Energy Harvesting and Dynamic Self-Powered Tactile Perception.

The technical synergy between flexible sensing paper and triboelectric nanogenerator (TENG) in the next stage of artificial intelligence Internet of Things engineering makes the development of intelligent sensing paper with triboelectric function very attractive. Therefore, it is extremely urgent to explore functional papers that are more suitable for triboelectric sensing. Here, a cellulose nanocrystals (CNCs) reinforced PVDF hybrid paper (CPHP) is developed by electrospinning technology. Benefitting from the unique effects of CNCs, CPHP forms a solid cross-linked network among fibers and obtains a high-strength (25 MPa) paper-like state and high surface roughness. Meanwhile, CNCs also improve the triboelectrification effect of CPHP by assisting the PVDF matrix to form more electroactive phases (96% share) and a higher relative permittivity (17.9). The CPHP-based TENG with single electrode configuration demonstrates good output performance (open-circuit voltage of 116 V, short-circuit current of 2.2 µA and power density of 91 mW m-2 ) and ultrahigh pressure-sensitivity response (3.95 mV Pa-1 ), which endows CPHP with reliable power supply and sensing capability. More importantly, the CPHP-based flexible self-powered tactile sensor with TENG array exhibits multifunctional applications in imitation Morse code compilation, tactile track recognition, and game character control, showing great prospects in the intelligent inductive device and human-machine interaction.

Acidic CO2 Electrolysis Addressing the "Alkalinity Issue" and Achieving High CO2 Utilization.

Electrochemical CO2 reduction reaction (CO2 RR) provides a promising approach for sustainable chemical fuel production of carbon neutrality. Neutral and alkaline electrolytes are predominantly employed in the current electrolysis system, but with striking drawbacks of (bi)carbonate (CO3 2- /HCO3 - ) formation and crossover due to the rapid and thermodynamically favourable reaction between hydroxide (OH- ) with CO2 , resulting in low carbon utilization efficiency and short-lived catalysis. Very recently, CO2 RR in acidic media can effectively address the (bi)carbonate issue; however, the competing hydrogen evolution reaction (HER) is more kinetically favourable in acidic electrolytes, which dramatically reduces CO2 conversion efficiency. Thus, it is a big challenge to effectively suppress HER and accelerate acidic CO2 RR. In this review, we begin by summarizing the recent progress of acidic CO2 electrolysis, discussing the key factors limiting the application of acidic electrolytes. We then systematically discuss addressing strategies for acidic CO2 electrolysis, including electrolyte microenvironment modulation, alkali cations adjusting, surface/interface functionalization, nanoconfinement structural design, and novel electrolyzer exploitation. Finally, the new challenges and perspectives of acidic CO2 electrolysis are suggested. We believe this timely review can arouse researchers' attention to CO2 crossover, inspire new insights to solve the "alkalinity problem" and enable CO2 RR as a more sustainable technology.

Functional Porous Ionic Polymers as Efficient Heterogeneous Catalysts for the Chemical Fixation of CO2 under Mild Conditions.

The development of efficient and metal-free heterogeneous catalysts for the chemical fixation of CO2 into value-added products is still a challenge. Herein, we reported two kinds of polar group (-COOH, -OH)-functionalized porous ionic polymers (PIPs) that were constructed from the corresponding phosphonium salt monomers (v-PBC and v-PBH) using a solvothermal radical polymerization method. The resulting PIPs (POP-PBC and POP-PBH) can be used as efficient bifunctional heterogeneous catalysts in the cycloaddition reaction of CO2 with epoxides under relatively low temperature, ambient pressure, and metal-free conditions without any additives. It was found that the catalytic activities of the POP-PBC and POP-PBH were comparable with the homogeneous catalysts of Me-PBC and PBH and were higher than that of the POP-PPh3-COOH that was synthesized through a post-modification method, indicating the importance of the high concentration catalytic active sites in the heterogeneous catalysts. Reaction under low CO2 concentration conditions showed that the activity of the POP-PBC (with a conversion of 53.8% and a selectivity of 99.0%) was higher than that of the POP-PBH (with a conversion of 32.3% and a selectivity of 99.0%), verifying the promoting effect of the polar group (-COOH group) in the porous framework. The POP-PBC can also be recycled at least five times without a significant loss of catalytic activity, indicating the high stability and robustness of the PIPs-based heterogeneous catalysts.

Efficient and Selective Electroreduction of CO2 to HCOOH over Bismuth-Based Bromide Perovskites in Acidic Electrolytes.

Metal halide perovskites, primarily used as optoelectronic devices, have not been applied for electrochemical conversion due to their insufficient stability in moisture. Herein, two bismuth-based perovskites are introduced as novel electrocatalysts to convert CO2 into HCOOH in aqueous acidic media (pH 2.5), exhibiting a high Faradaic efficiency for HCOOH of >80 % in a wide potential range from -0.75 to -1.25 V. Their structural evolution against water was dynamically monitored by in situ spectra. Theoretical calculations further reveal that the formation of intermediate OCHO* on bismuth sites of Cs3 Bi2 Br9 (111) play a pivotal role toward HCOOH production, which has a lower energy barrier than that on Cs2 AgBiBr6 (001) surfaces. Significantly, CO2 reacts with protons instead of water which can enhance CO2 reduction rate and suppress hydrogen evolution by avoiding carbonate formation in acidic electrolytes. This work paves the way for the extensive investigation of halide perovskites in aqueous systems.

The most active Cu facet for low-temperature water gas shift reaction.

Identification of the active site is important in developing rational design strategies for solid catalysts but is seriously blocked by their structural complexity. Here, we use uniform Cu nanocrystals synthesized by a morphology-preserved reduction of corresponding uniform Cu2O nanocrystals in order to identify the most active Cu facet for low-temperature water gas shift (WGS) reaction. Cu cubes enclosed with {100} facets are very active in catalyzing the WGS reaction up to 548 K while Cu octahedra enclosed with {111} facets are inactive. The Cu-Cu suboxide (CuxO, x ≥ 10) interface of Cu(100) surface is the active site on which all elementary surface reactions within the catalytic cycle proceed smoothly. However, the formate intermediate was found stable at the Cu-CuxO interface of Cu(111) surface with consequent accumulation and poisoning of the surface at low temperatures. Thereafter, Cu cubes-supported ZnO catalysts are successfully developed with extremely high activity in low-temperature WGS reaction.Nanocrystals display a variety of facets with different catalytic activity. Here the authors identify the most active facet of copper nanocrystals relevant to the low-temperature water gas shift reaction and further design zinc oxide-copper nanocubes with exceptionally high catalytic activity.

Crystal-plane-controlled selectivity of Cu(2)O catalysts in propylene oxidation with molecular oxygen.

The selective oxidation of propylene with O2 to propylene oxide and acrolein is of great interest and importance. We report the crystal-plane-controlled selectivity of uniform capping-ligand-free Cu2 O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O2 : Cu2 O octahedra exposing {111} crystal planes are most selective for acrolein; Cu2 O cubes exposing {100} crystal planes are most selective for CO2 ; Cu2 O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One-coordinated Cu on Cu2 O(111), three-coordinated O on Cu2 O(110), and two-coordinated O on Cu2 O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO2 , respectively. These results reveal that crystal-plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level.

In situ real-time diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) study of hydrogen adsorption and desorption on Ir/SiO2 catalyst.

The adsorption and desorption of hydrogen on Ir/SiO(2) catalyst were studied by using in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) combined with curve-fitting analysis. The results indicate that there are three different surface species formed on the catalyst that correspond to the peaks at 1950, 2010, and 2035 cm(-1), respectively, when exposed in H(2) flow at 130 °C. These surface species display different adsorption and desorption trends. Surface hydride forms after the catalyst is cooled to 80 °C and it disappears after the catalyst is heated to 130 °C again. This study may help us understand the interaction between hydrogen and noble metals and thus give more insights to heterogeneous catalytic mechanism involving hydrogen and hydrogen storage using metal materials.

Study of defect sites in Ce1-xMxO2-δ (x = 0.2) solid solutions using Raman spectroscopy.

A series of Ce(1-x)M(x)O(2-δ) (M = Gd, Zr, La, Sm, Y, Lu, and Pr) samples were characterized by Raman spectroscopy to investigate the evolution of defect sites (oxygen vacancies and MO(8)-type complex) and their distributions in the samples. It was found that the evolution of oxygen vacancies was due to the different ionic valence state of dopant from that of Ce(4+), while the evolution of the MO(8)-type complex was due to the different ionic radius of dopant from that of Ce(4+). The distributions of defect sites were investigated using 325 and 514 nm excitation laser lines, indicating that the defect sites were surface enriched. Moreover, the increasing ordering level of the sample led to a decline in the concentration of the MO(8)-type complex in the sample but the constant concentration of oxygen vacancies, implying that the metastable MO(8)-type complex species were more disordered compared to the oxygen vacancies.

UV and visible Raman studies of oxygen vacancies in rare-earth-doped ceria.

Surface properties of rare-earth (RE) doped ceria (RE = Sm, Gd, Pr, and Tb) were investigated by UV (325 nm) and visible (514, 633, and 785 nm) Raman spectroscopy, combined with UV-vis diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectra techniques. It was found that the optical absorption property of samples, the wavelength of detecting laser line, and the inhomogeneous distribution of the dopants significantly affected the obtained surface information, namely, the peak intensity and shape at ca. 460 and 570 cm(-1), as well as the observed oxygen vacancy concentration (A(570)/A(460)). The UV laser line detected the surface information of RE-doped ceria and disclosed the presence of many oxygen vacancies in the samples. The visible laser lines penetrated into the inner layer of the Sm- or Gd-doped CeO(2) and reflected the whole information of samples because of their weak absorptions of the visible laser. However, the Pr- or Tb-doped CeO(2) absorbed visible light strongly; thus, the laser can only determine the outer surface information of the sample.

Effect of optical absorbance on the Raman spectra of Ce(0.9)Tb(0.1)O(2-delta) solid solution.

Concentration of oxygen vacancies, optical absorption and microstructure of Ce(0.9)Tb(0.1)O(2-) (delta) material under different atmospheres (O(2), He and H(2)) and temperatures are characterized by in situ X-ray diffraction, in situ Raman spectroscopy and confocal microscopy. In this paper, we focus on how the change in optical absorption of the sample significantly affects the observed Raman information (peak intensity and the variation rule of oxygen vacancy concentration) under in situ conditions. With increasing temperature, the optical absorption of the sample decreases because of the release of oxygen and consequent changes of the microstructure. The decline in the optical absorption enables the Raman laser to increase its sampling depth, therefore, the deeper layer phonons in the structure are also sampled and contribute to the Raman scattering when the same excitation laser line is used. A more pronounced effect is observed when 514 nm laser line is used rather than 785 nm excitation, because both Tb and oxygen vacancies are enriched on the surface of the material and the 514 nm light provides surface information, while 785 nm light provides almost complete information on the sample.

In situ UV-vis and EPR study on the formation of hydroperoxide species during direct gas phase propylene epoxidation over Au/Ti-SiO(2) catalyst.

In recent years, there have been great experimental and theoretical advances in the understanding of the epoxidation of propylene by O(2) and H(2) over Au supported on titanium-containing oxidic supports; however, thus far spectroscopic evidence of reacting species for proposed mechanisms has been lacking. Hydroperoxide species have been postulated as an intermediate responsible for the epoxidation of propylene with O(2) and H(2). In order to obtain direct evidence for the different type of active oxygen species, in situ UV-vis and EPR measurements were carried out during the epoxidation of propylene with O(2) and H(2) over a Au/Ti-SiO(2) (Ti/Si = 3:100) catalyst. It was determined that the adsorbed species of oxygen (O(2)(-)) resided on Au, more likely at a perimeter site, and it led to the formation of titanium hydroperoxo species. These results support the possible mechanism of formation of these hydroperoxo species via H(2)O(2) produced from O(2) and H(2) adsorbed on the Au surfaces.