Tuning the compositions and structures of Pdbased nanomaterials and their supports has shown great potentials in facilitating the sluggish ethanol oxidation reaction (EOR) in alkaline direct ethanol fuel cells. Accordingly, a facile solvothermal method involving Cu and Pd composition migrations is developed in this study, to synthesize highly uniform and small-sized nanospheres (NSs) possessing the special structures of composition-graded (CG) Cu 1 Pd 1 and surface-doped (SD) Ir 0.03 , which are evenly anchored onto N-doped porous graphene (NPG) as a highperformance EOR electrocatalyst ( CG Cu 1 Pd 1 / SD Ir 0.03 NSs/ NPG). Comprehensive physicochemical characterizations, electrochemical analyses, and first-principles calculations reveal that, benefiting from the NPG-imparted mass-transfer and oxygen-reduction effects, the CG−SD structural and sizemorphology effects of the NS, as well as the Cu-and Ir-induced bifunctional, geometric, and ligand effects, CG Cu 1 Pd 1 / SD Ir 0.03 NSs/NPG exhibits not only ultrahigh electrocatalytic activity and highly efficient noble-metal (NM) utilization, showing 7105 and 6685 mA mg −1 in Pd-and NM-mass-specific activity (MSA), respectively, which are 15.8 and 14.9 times those of commercial Pd/C, but also satisfactory electrocatalytic durability, retaining respective 28.1-and 19.2-fold enhancements in Pd-MSA compared to the commercial Pd/C, after 1 h chronoamperometric and 500-cycle potential cycling degradation tests. This study not only provides an effective and versatile synthetic strategy to prepare the NM-efficient metal-based nanomaterials with the special CG and SD structures for various electrocatalytic and energy-conversion applications, but also proposes some insights into the composition-and structure-function relations in EOR electrocatalytic mechanism for rationally designing highly active and durable EOR electrocatalysts.

In this study, FeCl3, AlCl3, CaCl2, and kaolinite were selected as model soil minerals and incubated with walnut shell derived biochar for 3 months and the incubated biochar was then separated for the investigation of biochar-mineral interfacial behavior using XRD and SEM-EDS. The XPS, TGA, and H2O2 oxidation were applied to evaluate effects of the interaction on the stability of biochar. Fe8O8(OH)8Cl1.35 and AlCl3·6H2O were newly formed on the biochar surface or inside of the biochar pores. At the biochar-mineral interface, organometallic complexes such as Fe-O-C were generated. All the 4 minerals enhanced the oxidation resistance of biochar surface by decreasing the relative contents of C-O, C═O, and COOH from 36.3% to 16.6-26.5%. Oxidation resistance of entire biochar particles was greatly increased with C losses in H2O2 oxidation decreasing by 13.4-79.6%, and the C recalcitrance index (R50,bicohar) in TGA analysis increasing from 44.6% to 45.9-49.6%. Enhanced oxidation resistance of biochar surface was likely due to the physical isolation from newly formed minerals, while organometallic complex formation was probably responsible for the increase in oxidation resistance of entire biochar particles. Results indicated that mineral-rich soils seemed to be a beneficial environment for biochar since soil minerals could increase biochar stability, which displays an important environmental significance of biochar for long-term carbon sequestration.

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This review provides exhaustive insights into material and process design of adsorption-based direct air capture in the past five years.

It has been reported that zerovalent iron can help biochar improve efficiency in heavy metal (HM) absorption, but the surface chemical behaviors and HM removal mechanisms remain unclear. We successfully synthesized the magnetic nanoscale zerovalent iron assisted biochar (nZVI-BC). The porosity, crystal structure, surface carbon/iron atom state, and element distribution were comprehensively investigated to understand nZVI-BC’s interfacial chemical behaviors and HM removal mechanisms. We clearly revealed the formation of a nanoscale Fe0 core–Fe3O4 shell on the surface/pores/channels of biochar. With the combination of iron nanoparticles and biochar, C–O/COOH groups were cracked with the formation of CO/CC, indicating the C–O–Fe acted as an electron acceptor during the reduction reaction. We also demonstrated that the stabilization was dramatically improved in the nZVI-BC, while more reduced iron and better homogeneity were observed. These results, showing the surface chemical behaviors of nZVI-BC, would help increase our understanding of the HM removal mechanisms. Moreover, our demonstration of the superior removal ability of multiple HM (Pb2+, Cd2+, Cr6+, Cu2+, Ni2+, Zn2+) from a solution can provide a breakthrough in making a feasible material for removing HM from polluted water resources.

The wide distribution and high heterogeneity of different elements in biochars derived from diverse feedstocks make it difficult to regulate their application in soil and to evaluate the maximum potential contribution of the nutrients and trace metals as well as the potential risk of toxic metals. This study classified 20 biochars, covering six typical categories, into three clusters according to their similarity and distance on nutrients and minerals using cluster analysis. Four principle components (PC) were extracted using factor analysis to reduce dimension and clearly characterize the mineral profile of these biochars. The contribution of each group of elements in the PCs to every cluster was clarified. PC1 had a high loading for Mg, Cu, Zn, Al, and Fe; PC2 was related to N, K, and Mn; and PC3 and PC4 mainly represented P and Ca. Cluster 1 included bone dregs and eggshell biochars with PC3 and PC4 as the main contributors. Cluster 2 included waterweeds and waste paper biochars, which were close to shrimp hull and chlorella biochars, with the main contributions being from PC2 and PC4. Cluster 3 included biochars with PC1 as the main contributor. At a soil biochar amendment rate of 50 t ha, the soil nutrients were significantly elevated, whereas the rise in toxic metals was negligible compared with Class I of the China Environmental Quality Standards for Soil. Biochar can potentially supply soil nutrients and trace metals, and different cluster biochars can be applied appropriately to different soils so that excessive or deficient nutrient and metal applications can be avoided.

As the fundamental structural protein in mammals, collagen transmits cyclic forces that are necessary for the mechanical function of tissues, such as bone and tendon. Although the tissue-level mechanical behavior of collagenous tissues is well understood, the response of collagen at the nanometer length scales to cyclical loading remains elusive. To address this major gap, we cyclically stretched individual reconstituted collagen fibrils, with average diameter of 145 ± 42 nm, to small and large strains in the partially hydrated conditions of 60% relative humidity. It is shown that cyclical loading results in large steady-state hysteresis that is reached immediately after the first loading cycle, followed thereafter by limited accumulation of inelastic strain and constant initial elastic modulus. Cyclic loading above 20% strain resulted in 70% increase in tensile strength, from 638 ± 98 MPa to 1091 ± 110 MPa, and 70% increase in toughness, while maintaining the ultimate tensile strain of collagen fibrils not subjected to cyclic loading. Throughout cyclic stretching, the fibrils maintained a steady-state hysteresis, yielding loss coefficients that are 5-10 times larger than those of known homogeneous materials in their modulus range, thus establishing damping of nanoscale collagen fibrils as a major component of damping in tissues. STATEMENT OF SIGNIFICANCE: It is shown that steady-state energy dissipation occurs in individual collagen fibrils that are the building blocks of hard and soft tissues. To date, it has been assumed that energy dissipation in tissues takes place mainly at the higher length scales of the tissue hierarchy due to interactions between collagen fibrils and fibers, and in limited extent inside collagen fibrils. It is shown that individual collagen fibrils need only a single loading cycle to assume a highly dissipative, steady-state, cyclic mechanical response. Mechanical cycling at large strains leads to 70% increase in mechanical strength and values exceeding those of engineering steels. The same cyclic loading conditions also lead to 70% increase in toughness and loss properties that are 5-10 times higher than those of engineering materials with comparable stiffness.

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