Extra-High CO2 Adsorption and Controllable C2H2/CO2 Separation Regulated by the Interlayer Stacking in Pillar-Layered Metal-Organic Frameworks.

Pillar-layered metal-organic frameworks (PLMOFs) are promising gas adsorbents due to their high designability. In this work, high CO2 storage capacity as well as controllable C2H2/CO2 separation ability are acquired by rationally manipulating the interlayer stacking in pillar-layered MOF materials. The rational construction of pillar-layered MOFs started from the 2D Ni-BTC-pyridine layer, an isomorphic structure of pioneering MOF-1 reported in 1995. The replacement of terminal pyridine groups by bridging pyrazine linkers under optimized solvothermal conditions led to three 3D PLMOFs with different stacking types between adjacent Ni-BTC layers, named PLMOF 1 (ABAB stacking), PLMOF 2 (AABB stacking), and PLMOF 3 (AAAA stacking). Regulated by the layer arrangements, CO2 and C2H2 adsorption capacities (273 K and 1 bar) of PLMOFs 1-3 vary from 173.0/153.3, 185.0/162.4, to 203.5/159.5 cm3 g-1, respectively, which surpass the values of most MOF adsorbents. Dynamic breakthrough experiments further indicate that PLMOFs 1-3 have controllable C2H2/CO2 separation performance, which can successfully overcome the C2H2/CO2 separation challenge. Specially, PLMOFs 1-3 can remove trace CO2 (3%) from the C2H2/CO2 mixture and produce high-purity ethylene (99.9%) in one step with the C2H2 productivities of 1.68, 2.45, and 3.30 mmol g-1, respectively. GCMC simulations indicate that the superior CO2 adsorption and unique C2H2/CO2 separation performance are mainly ascribed to different degrees of CO2 agglomeration in the ultramicropores of these PLMOFs.

Maximizing Electrostatic Interaction in Ultramicroporous Metal-Organic Frameworks for the One-Step Purification of Acetylene from Ternary Mixture.

Developing efficient adsorbents for acetylene purification from multicomponent mixtures is of critical significance in the chemical industry, but the trade-off between regenerability and selectivity significantly restricts practical industrial applications. Here, we report ultramicroporous metal-organic frameworks with acetylene-affinity channels to enhance electrostatic interaction between C2H2 and frameworks for the efficient one-step purification of C2H2 from C2H2/CO2/C2H4 mixtures, in which the electrostatic interaction led to high regenerability. The obtained SNNU-277 exhibits significantly higher adsorption capacity for C2H2 than that for both C2H4 and CO2 at 298 K and 0.1 bar, while an ultrahigh selectivity of C2H2/C2H4 (100.6 at 298 K) and C2H2/CO2 (32.8 at 298 K) were achieved at 1 bar. Breakthrough experiments validated that SNNU-277 can efficiently separate C2H2 from C2H2/C2H4/CO2 mixtures. CO2 and C2H4 broke through the adsorption column at 4 and 14.8 min g-1, whereas C2H2 was detected until 177.6 min g-1 at 298 K. Theoretical calculations suggest that the framework is electrostatically compatible with C2H2 and electrostatically repels C2H4 and CO2 in the mixed components. This work highlights the importance of rational pore engineering for maximizing the electrostatic effect with the preferentially absorbed guest molecule for efficient multicomponent separation.

High-Valence Metal Doping Induced Lattice Expansion for M-FeNi LDH toward Enhanced Urea Oxidation Electrocatalytic Activities.

The precise design of low-cost, efficient, and definite electrocatalysts is the key to sustainable renewable energy. The urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction for energy-saving hydrogen generation. In this study, by tuning the lattice expansion, a series of M-FeNi layered double hydroxides (M-FeNi LDHs, M: Mo, Mn, V) with excellent UOR performance are synthesized. The hydrolytic transformation of Fe-MIL-88A is assisted by urea, Ni2+ and high-valence metals, to form a hollow M-FeNi LDH. Owing to the large atomic radius of the high-valence metal, lattice expansion is induced, and the electronic structure of the FeNi-LDH is regulated. Doping with high-valence metal is more favorable for the formation of the high-valence active species, NiOOH, for the UOR. Moreover, the hollow spindle structure promoted mass transport. Thus, the optimal Mo-FeNi LDH showed outstanding UOR electrocatalytic activity, with 1.32 V at 10 mA cm-2 . Remarkably, the Pt/C||Mo-FeNi LDH catalyst required a cell voltage of 1.38 V at 10 mA·cm-2 in urea-assisted water electrolysis. This study suggests a new direction for constructing nanostructures and modulating electronic structures, which is expected to ultimately lead to the development of a class of auxiliary electrocatalysts.

Development of a Mixed Multinuclear Cluster Strategy in Metal-Organic Frameworks for Methane Purification and Storage.

Metal-organic frameworks (MOFs) have attracted extensive attention in methane (CH4) purification and storage. Specially, multinuclear cluster-based MOFs usually have prominent performance because of large cluster size and abundant open metal sites. However, compared to diverse combinations of organic linkers, one MOF with two or more multinuclear clusters is difficult to achieve. In this paper, we demonstrate a mixed multinuclear cluster strategy, which successfully led to three new heterometallic MOFs (SNNU-328-330) with the same common H3TATB [2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine] tritopic linker and six types of multinuclear clusters ([YCd(COO)4(µ2-H2O)], [YCd2(COO)8], [In3(COO)6(µ3-OH)], [In3Eu2(COO)9(µ3-OH)3(µ4-O)], [Y9(COO)12(µ3-OH)14] and [Y2Cd8(COO)16(µ2-H2O)4(µ3-OH)8]). Three MOF adsorbents all show great potentials to remove the impurities (CO2 and C2-hydrocarbons) in natural gas and show prominent high-pressure methane storage capacity. Among them, the ideal adsorbed solution theory separation ratios of equimolar C2H2/CH4, C2H4/CH4, C2H6/CH4, and CO2/CH4 at 298 K for SNNU-328 reach to 29.7-16.0, 19.1-8.2, 33.2-10.3, and 74.3-8.5, which have surpassed many famous MOF adsorbents. Dynamic breakthrough experiments conducted at 273 and 298 K showed that SNNU-330 can separate CH4 from C2H2/CH4, C2H4/CH4, C2H6/CH4, and CO2/CH4 mixtures with the breakthrough interval times of about 48.2, 17.9, 37.2, and 17.1 min g-1 (273 K, 1 bar, v/v = 50/50, 2 mL min-1), respectively. Remarkably, SNNU-329 exhibits extremely high methane storage performance at 298 K with the total uptake and working capacity of 192 cm3 cm-3 (95 bar) and 171 cm3 cm-3 (65 bar) due to the synergistic effects of high surface area, suitable pore sizes, and multiple open metal sites.

How does renewable energy, newborn birth rates, industrialization, and economic growth affect environmental quality? New evidence from 90 Belt and Road countries.

Reducing carbon emissions is a critical approach for attaining global environmental sustainability and combating climate change. To investigate how energy, population, industry, and economic structure affect environmental quality. This study collects panel data for 90 Belt and Road (B&R) nations from 1995 to 2021. For the first time, the nonlinear dynamic impacts of renewable energy, newborn birth rate, industrialization, and economic growth on carbon emissions are investigated using a threshold panel model and a panel vector autoregression (PVAR) model. According to the study's findings: (1) models 1-4 demonstrate that all structural factors have substantial threshold impacts on carbon emissions, demonstrating a nonlinear connection. (2) Carbon emissions are negatively impacted by energy structure (renewable energy) and population structure (newborn birth rate). Industrial structure (industrialization) and economic structure (economic growth), on the other hand, have a beneficial influence on carbon emissions. However, when the structural variables grow in size, their threshold effects all increase this contribution. (3) In three groups of nations with varying wealth levels, differences in the influence intensity of structural factors on carbon emissions, particularly renewable energy and economic growth, were detected. The impact of renewable energy on carbon emissions is: middle-income (MI) countries > high-income countries (HI) > low-income countries (LI). The impact of economic growth on carbon emissions is MI countries > LI countries > HI countries. Based on the findings, relevant policy recommendations are provided to the policy makers of the "B&R" countries from the perspectives of structural factors and heterogeneity. It provides certain references for the realization of global environmentally sustainable development strategies and the coordinated development of economic, social and environmental systems.

Precise Introduction of Single Vanadium Site into Indium-Organic Framework for CO2 Capture and Photocatalytic Fixation.

The capture and fixation of CO2 under mild conditions is a cost-effective route to reduce greenhouse gases, but it is challenging because of the low conversion and selectivity issues. Metal-organic frameworks (MOFs) are promising in the fields of adsorption and catalysis because of their structural tunability and variability. However, the precise structural design of MOFs is always pursued and elusive. In this work, a metal-mixed MOF (SNNU-97-InV) was designed by precisely introducing single vanadium site into the isostructural In-MOF (SNNU-97-In). The single V sites clearly change the interactions between the MOF framework and CO2 molecules, leading to a 71.3% improvement in the CO2 adsorption capacity. At the same time, the enhanced light absorption enables SNNU-97-InV to efficiently convert CO2 into cyclic carbonates (CCs) with epoxides under illumination. Controlled experiments showed that the promoted performance of SNNU-97-InV may be that the V═O site can more easily combine with CO2 and convert them into an intermediate state under illumination, and the possible mechanism was thus speculated.

Photoelectrochemical Performance Improving Mechanism: Hybridization Appearing at the Energy Band of BiVO4 Photoanode by Doped Quantum Layers Modification.

Surface passivation of the photoelectrode by wide bandgap semiconductor quantum layer is an important strategy to improve work stability and surface state inhibition. However, an inevitable energy barrier is generated during the quantum tunneling process of the photocarriers. To overcome this shortage, a tandem photo-generated hole transfer route is fabricated on BiVO4 photoanode by doped dual-quantum layers modification, Ni-ZnO (5 nm) and Rh-SrTiO3 (≈10 nm). Modulated photoelectrochemical (PEC), Scanning Kelvin Probe (SKP), and DFT calculation method results indicate that a tandem hole ohmic contact route is formed in the photoanode to reduce the quantum tunneling energy barrier, meanwhile, the photon absorption capacity of BiVO4 is improved after doped quantum layers modification. Both a phenomenal attribute to the energy band hybridization between Ni, Rh 3d orbits in quantum layers with BiVO4 photoanode. Then, the modified BiVO4 photoanode achieves the recoded photocurrent density of 6.47 and 5.18 mA cm-2 (Na2 SO3 electrolyte, VRHE  = 1.23 V) under simulated sun light (100 mW cm-2 AM 1.5 G) by xenon lamp illumination without and with UV composition cutting down to ≈5%, respectively. Generally, this work will highlight a potential application in the fields of PEC water splitting and photovoltaic conversion for various semiconductor nanomaterials.

Control of Thermal Conductance across Vertically Stacked Two-Dimensional van der Waals Materials via Interfacial Engineering.

A comprehensive understanding of the roles of various nanointerfaces in thermal transport is of critical significance but remains challenging. A two-dimensional van der Waals (vdW) heterostructure with tunable interface lattice mismatch provides an ideal platform to explore the correlation between thermal properties and nanointerfaces and achieve controllable tuning of heat flow. Here, we demonstrate that interfacial engineering is an efficient strategy to tune thermal transport via systematic investigation of the thermal conductance (G) across a series of large-area four-layer stacked vdW materials using an improved polyethylene glycol-assisted time-domain thermoreflectance method. Owing to its rich interfacial mismatch and weak interfacial coupling, the vertically stacked MoSe2-MoS2-MoSe2-MoS2 heterostructure demonstrates the lowest G of 1.5 MW m-2 K-1 among all vdW structures. A roadmap to tune G via homointerfacial mismatch, interfacial coupling, and heterointerfacial mismatch is further demonstrated for thermal tuning. Our work reveals the roles of various interfacial effects on heat flow and highlights the importance of the interfacial mismatch and coupling effects in thermal transport. The design principle is also promising for application in other areas, such as the electrical tuning of energy storage and conversion and the thermoelectricity tuning of thermoelectronics.

Interfacial Engineering of W2 N/WC Heterostructures Derived from Solid-State Synthesis: A Highly Efficient Trifunctional Electrocatalyst for ORR, OER, and HER.

To meet the practical demand of overall water splitting and regenerative metal-air batteries, highly efficient, low-cost, and durable electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are required to displace noble metal catalysts. In this work, a facile solid-state synthesis strategy is developed to construct the interfacial engineering of W2 N/WC heterostructures, in which abundant interfaces are formed. Under high temperature (800 °C), volatile CNx species from dicyanodiamide are trapped by WO3 nanorods, followed by simultaneous nitridation and carbonization, to form W2 N/WC heterostructure catalysts. The resultant W2 N/WC heterostructure catalysts exhibit an efficient and stable electrocatalytic performance toward the ORR, OER, and HER, including a half-wave potential of 0.81 V (ORR) and a low overpotential at 10 mA cm-2 for the OER (320 mV) and HER (148.5 mV). Furthermore, a W2 N/WC-based Zn-air battery shows outstanding high power density (172 mW cm-2 ). Density functional theory and X-ray absorption fine structure analysis computations reveal that W2 N/WC interfaces synergistically facilitate transport and separation of charge, thus accelerating the electrochemical ORR, OER, and HER. This work paves a novel avenue for constructing efficient and low-cost electrocatalysts for electrochemical energy devices.

B, N-dual doped sisal-based multiscale porous carbon for high-rate supercapacitors.

B, N dual-doped sisal-based activated carbon (BN-SAC) with a multiscale porous structure for high-rate supercapacitor electrode was prepared through a novel and facile strategy. With the inherent cellular channels serving as primary macropores, secondary mesopores and micropores are generated on the fiber surface and tracheid walls through low-pressure rapid carbonization of (NH4)2B4O7-containing sisal fibers and successive KOH activation. In addition to introducing B, N atoms into the BN-SAC, the additive also facilitates the formation of mesopores due to the rapid gas evaporation during its decomposition, leading to significantly increased specific surface area (2017 m2 g-1) and mesoporosity (68.6%). As a result, the BN-SAC-3 shows highly enhanced electrochemical performance including a high specific capacitance of 304 F g-1, excellent rate capability (with 72.6% retention at 60 A g-1) and superior cycling stability (4.6% capacitance loss after 3000 cycles). After assembling the BN-SAC-3 into symmetric supercapacitor, it shows a specific capacitance of 258 F g-1 at 1 A g-1 with 76.4% retention at 40 A g-1 in 6 M KOH electrolyte, and delivers a maximum energy density of 24.3 W h kg-1 at a power density of 612.8 W kg-1 in 1 M TEABF4/AN electrolyte. This work provides a new strategy for the synthesis of multiscale porous ACs for high-performance supercapacitors or other energy storage and conversion devices and is expected to be applied on other biomasses for large-scale production.

Correction: B, N-dual doped sisal-based multiscale porous carbon for high-rate supercapacitors.

[This corrects the article DOI: 10.1039/C8RA09663E.].

Laminated Hybrid Junction of Sulfur-Doped TiO2 and a Carbon Substrate Derived from Ti3C2 MXenes: Toward Highly Visible Light-Driven Photocatalytic Hydrogen Evolution.

TiO2 is an ideal photocatalyst candidate except for its large bandgap and fast charge recombination. A novel laminated junction composed of defect-controlled and sulfur-doped TiO2 with carbon substrate (LDC-S-TiO2/C) is synthesized using the 2D transition metal carbides (MXenes) as a template to enhance light absorption and improve charge separation. The prepared LDC-S-TiO2/C catalyst delivers a high photocatalytic H2 evolution rate of 333 µmol g-1 h-1 with a high apparent quantum yield of 7.36% at 400 nm and it is also active even at 600 nm, resulting into a 48 time activity compared with L-TiO2/C under visible light irradiation. Further theoretical modeling calculation indicates that such novel approach also reduces activation energy of hydrogen production apart from broadening the absorption wavelength, facilitating charge separation, and creating a large surface area substrate. This synergic effect can also be applied to other photocatalysts' modification. The study provides a novel approach for synthesis defective metal oxides based hybrids and broaden the applications of MXene family.

One-dimensional hierarchical MoO2-MoSx hybrids as highly active and durable catalysts in the hydrogen evolution reaction.

The hydrogen evolution reaction (HER) is a fundamental process in electrocatalysis and plays an important role in energy conversion through water splitting to produce hydrogen. Finding highly effective and scalable HER catalysts is becoming a very urgent task. In this work, we developed a facile method to synthesize a one-dimensional hierarchical MoO2-MoSx hybrid electrocatalyst via the calcination of a one-dimensional (1D) organic-inorganic MoO3-EDA precursor. The obtained MoO2-MoSx hybrids deliver a low onset potential of 155 mV, a low Tafel slope of 51.6 mV dec-1 and excellent cycling stability in acidic electrolytes, suggesting high electrocatalytic activity. Furthermore, MoO2-MoS2 exhibited high cycling stability even after 10 h of continuous operation under high overpotential; the current density still remained unchanged. The enhanced HER performances are likely due to high conductivity and more exposed active sites and the effective integration of MoO2 and MoSx. In a word, these results fully demonstrated that 1D nanostructured MoO2-MoSx hybrid materials may have great potential in future clean energy applications.

One-step synthesis of 2D-layered carbon wrapped transition metal nitrides from transition metal carbides (MXenes) for supercapacitors with ultrahigh cycling stability.

A novel one-step method to synthesize 2D carbon wrapped TiN (C@TiN) was proposed via using 2D metal carbides (MXenes) as precursors. This study provides a novel approach to synthesize carbon wrapped metal nitrides.

Surface engineering-modulated porous N-doped rod-like molybdenum phosphide catalysts: towards high activity and stability for hydrogen evolution reaction over a wide pH range.

Electrochemical water splitting is an economic, green and sustainable route to produce hydrogen through the hydrogen evolution reaction (HER). Nowadays, noble metal-free phosphides have been widely used as catalysts in the HER, showing potential applications for both renewable energy production and environmental remediation. Nevertheless, developing surface self-doped MoP electrocatalysts with high HER performances in a wide pH range still remains a challenge. In this work, a novel synthesis strategy was developed to fabricate porous one-dimensional (1D) nitrogen-doped molybdenum phosphide (N-MoP) nanorods. The prepared N-MoP-800 catalyst exhibits a low onset potential of 65 mV and low Tafel slope of 58.66 mV dec-1 in 0.5 M H2SO4, which is almost 2 times higher than that of the pristine MoP nanorod anode. Furthermore, the N-MoP materials show long-term durability for 12 h in a wide pH range. The synergistic effects of pyridinic N and N doping in MoP are responsible for the high catalytic activity of N-MoP under acidic conditions, while the N-Mo component plays a key role in enhancing the HER activity of N-MoP. These interesting findings are helpful for the rational design of highly active HER catalysts. More importantly, this study provides a new strategy to synthesize highly active catalysts with low costs for clean energy conversion.

[Correlation Between Functional Groups and Radical Scavenging Activities of Acidic Polysaccharides from Dendrobium].

OBJECTIVE: To compare the radical scavenging activity of five different acidic polysaccharides, and to find the correlation with the functional groups. METHODS: Alkali extraction method and Stepwise ethanol precipitation method were used to extract and concentrate the five Dendrobium polysaccharides, and to determine the contents of sulfuric acid and uronic acid of each kind of acidic polysaccharides, and the scavenging activity to ABTS+ radical and hydroxyl radical. Functional group structures were examined by FTIR Spectrometer. RESULTS: Five kinds of Dendrobium polysaccharides had different ability of scavenging ABTS+ free radical and hydroxyl free radical. Moreover, the study had shown that five kinds of antioxidant activity of acidic polysaccharides had obvious correlation withuronic acid and sulfuric acid. The antioxidant activity of each sample was positively correlated with the content of uronic acid, and negatively correlated with the content of sulfuric acid. CONCLUSION: Sulfuric acid can inhibit the antioxidant activity of acidic polysaccharide but uronic acid can enhance the free radical scavenging activity. By analyzing the structure characteristics of five acidic polysaccharides, all samples have similar structures, however, Dendrobium denneanum, Dendrobium devonianum and Dendrobium officinale which had ß configuration have higher antioxidant activity than Dendrobium nobile and Dendrobium fimbriatum which had a configuration.