Aug 2026· Angewandte Chemie· pp.
e3493135
· 0 citations· 31 references
Medicine
Abstract
Fossil-derived diesel raises sustainability and air-quality concerns, motivating biomass-based alternatives; however, current biodiesel routes suffer from food-fuel competition, poor fuel properties, and energy-intensive upgrading. Electrocatalytic C─C coupling of biomass molecules followed by hydrodeoxygenation (HDO) offers a cleaner pathway, yet has been limited to dimer formation. Here, we successfully resolved this longstanding bottleneck through construction of Pd1Cu single-atom alloy electrocatalyst, a trimer of 5-hydroxymethylfurfural is obtained with 44.7% selectivity. The combined oligomer (dimer and trimer) selectivity reaches 95.0% with 93.2% Faradaic efficiency, production rate achieves a record high of ∼50 g gcat -1 h-1. Subsequent HDO converts the oligomers into heteroatom-free n-dodecane and n-octadecane diesel blendstocks. Operando spectroscopy reveals a surface-confined ketyl-radical pathway in which isolated Pd atoms regulate hydrogen-atom supply and substrate adsorption, favoring C─C coupling over hydrogenation. This work establishes an electricity-driven route for controlled carbon-chain growth from biomass platforms.
Electrochemical green ammonia (NH3) production using renewable electricity is sustainable but suffers from selectivity-activity-stability trade-off under industrial conditions. Here we report an atomic interface engineering strategy enabling in-situ assembly and coupling of hexaethynylbenzenes on molybdenum-copper oxidesto form an sp-hybridized Mo/Cu-C≡C heterointerface. It features dual d-orbital hybridization (Mo 4d-C 2p and Cu 3d-C 2p) weakening N–O bond by 36.85% and lowering activation barrier by 0.43 eV, reversible electron-buffer facilitating proton-coupled electron transfer, and self-regulated charge compensation between metal atoms and -C≡C- atomic wires, collectively endowing high activity and near-complete hydrogen evolution reaction suppression. The resulting catalyst achieves high NH3 yielding rate (YNH3, 2.45 mmol h−1 cm−2) and Faradaic efficiency (~100%) under ambient conditions. A prototype flow electrolyzer operating with this catalyst sustains industrial-current densities of 500 mA cm−2 for 300 hours with <3% activity decay, yielding potable water from nitrate wastewater. The membrane electrode assembly (MEA) achieves 380 h stable operation at the same current density with YNH3 of 3.64 mmol h−1 cm−2. Converting nitrate-polluted water into ammonia offers a sustainable alternative to the Haber-Bosch process. Here, authors report a catalyst with sp-C~metal bonds that achieves high selectivity and stability at high currents, enabling fertilizer production and water purification.
Electrochemical glycerol oxidation offers a sustainable pathway for valorizing biodiesel-derived glycerol while lowering the energy demand of hydrogen production. However, Co-based catalysts are often limited by inefficient coupling between the electrochemical generation and chemical consumption of oxidized Co species. Herein, a urea-mediated strategy is developed to simultaneously tailor the morphology, surface electronic structure, and local structural order of Co3O4 electrodes. Urea directs the formation of vertically aligned nanoflakes, introduces Co-N coordination, increases the surface Co3+/Co2+ ratio, and generates defect-rich crystalline-amorphous interfacial regions. The optimized Co3O4/NF-5 electrode delivers 1000 mA cm-2 at 1.39 ± 0.02 V, maintains a formate Faradaic efficiency above 84.1 ± 1.4% over 1.3-1.8 V, and exhibits only 3.1% activity decay after 5000 cycles. Electrochemical kinetic analysis, in situ Raman spectroscopy, and potential-step measurements reveal efficient electrochemical-chemical turnover mediated predominantly by CoOOH species, with transient Co4+-associated species potentially contributing at elevated potentials. Density functional theory calculations further indicate that N incorporation modulates Co 3d states and strengthens reactant adsorption. An integrated electrolyzer operates continuously for 216 h, demonstrating device-level durability and favorable preliminary techno-economic prospects. These findings establish coupled morphological and electronic regulation as an effective strategy for promoting electrochemical-chemical turnover in glycerol electrooxidation.
Jingyi Zhang, Yuwei Li, Zongyao Guo et al.· Journal of Colloid and Inter...· 0 citations
Branched C8-C16 alkanes are highly desirable sustainable aviation fuel (SAF) components, as they confer low freezing points and favorable combustion properties. Currently, these alkanes are produced predominantly via the hydroprocessed esters and fatty acids (HEFA) pathway, which requires harsh hydrogenation and hydroisomerization conditions that often promote cracking and carbon loss, resulting in high energy consumption and limited yields (20-40 %). Here, we present a mild electrocatalytic strategy that converts bio-derived C2-C4 fatty acids and methyl acrylate into C8-C16 branched alkanes. Using a platinum electrode at ambient pressure and ice-bath temperature, this strategy integrates radical addition, hydrolysis, and decarboxylative coupling in a tandem sequence to achieve efficient carbon-chain growth from short-chain feedstocks. In contrast to HEFA, the process is driven by electrochemical radical generation and selective C-C bond formation rather than hydrogenation, thereby avoiding external H2 and suppressing the cracking reactions. As a result, the target branched alkanes are obtained in yields of up to 72.5 %, while the mild operating conditions also substantially reduce both energy input and carbon footprint. This work establishes a mild electrosynthetic paradigm for upgrading bio-based chemicals into SAF-range branched alkanes, thereby offering a complement to mainstream HEFA technology.
Xinyu Yang, Demeng Liu, Siyu Pan et al.· Bioresource Technology· 0 citations
Biomass is an abundant renewable carbon resource for the sustainable production of fuels and value-added chemicals. Electrocatalytic hydrogenation (ECH) provides a mild and attractive route for upgrading biomass-derived molecules without the need for externally supplied high-pressure H2. However, the structural complexity and multifunctionality of biomass substrates give rise to intricate reaction networks, while the competing hydrogen evolution reaction (HER) often limits Faradaic efficiency and product selectivity. In recent years, alloy-based catalysts have attracted increasing attention because of their outstanding hydrogenation performance in biomass electrocatalysis. This review summarizes recent progress in alloy-based catalysts for the ECH of biomass-derived molecules, covering phenolic compounds, aldehydes, and lignin-related substrates. Emphasis is placed on mechanistic understanding, including Langmuir-Hinshelwood and proton-coupled electron transfer pathways, as well as on structure-activity/selectivity relationships. Key challenges and future opportunities are also discussed from the perspectives of mechanism-guided catalyst design, electrolyte and reactor engineering, and the upgrading of complex biomass feedstocks.
Electrocatalytic hydrogenation (e -H) provides a sustainable route for converting unsaturated organic substrates under mild conditions using renewable electricity as the driving force. Here, we report an MOF-derived cobalt catalyst for the e -H of acetone and pyridine. A new two-dimensional cobalt metal-organic framework, Co-L0-NS, composed of Co(II) nodes and polyaromatic carboxylate linkers, was synthesized as nanosheets and used as a precursor to generate the active catalyst under cathodic bias. Electrochemical pretreatment induces controlled framework reconstruction to form MD-Cat, a highly dispersed, structurally disordered, Co(OH)2-rich nanocluster material. MD-Cat catalyzes the e -H of acetone to isopropanol with nearly quantitative Faradaic efficiency at optimized potentials and promotes pyridine hydrogenation to piperidine with up to 50% Faradaic efficiency. Comparative studies with electrodeposited cobalt, commercial cobalt nanoparticles, and bulk Co(OH)2 show that the MOF-derived catalyst exhibits superior current densities and product selectivity, which we attribute to its nanoscale morphology and hydroxylated cobalt environment. In situ Co K-edge XAS, XPS, PXRD, ATR-SEIRAS, and STEM analyses indicate that Co remains predominantly in the +2 oxidation state during catalysis while undergoing structural reorganization. Tafel analysis supports a PCET-type mechanism for acetone hydrogenation; while DFT calculations suggest that the Co/Co(OH)2 interface suppresses HER by weakening H* binding while preserving organic-substrate activation. These results highlight MOF-templated electrochemical reconstruction as a promising approach for designing selective e -H catalysts, not only by increasing catalyst accessibility through nanostructuring but also by enabling the formation of unique catalytic motifs that would otherwise be difficult to access using traditional methods.
B. K. Behera, Xin Zheng, Haomiao Xie et al.· Journal of the American Chem...· 0 citations
The electrochemical reduction of nitrate (NO3 -) offers a green and sustainable approach for treating nitrogen-containing wastewater and is regarded as a promising alternative to the energy-intensive Haber-Bosch process. However, this reaction entails multielectron transfer and complex reaction pathways, and its efficiency is often hampered by competing side reactions such as the hydrogen evolution reaction, as well as challenges related to the safe storage and transport of products. These limitations underscore the urgent need to develop electrocatalysts that exhibit high activity, stability, and selectivity. Since their emergence, single-atom catalysts (SACs) have attracted extensive interest due to their exceptional atomic utilization efficiency and relatively low cost. To elucidate the structure-performance relationships and underlying catalytic mechanisms of SACs in nitrate electroreduction, this review summarizes recent advances in SAC-based electrocatalysts, highlighting various categories of single-atom materials and their corresponding design strategies. Finally, we outline future research directions for SACs in this field, with the aim of providing valuable insights and guidance for the rational design of efficient, low-energy, and environmentally benign electrocatalytic nitrate reduction systems toward practical industrial applications.