Electrochemical Biomass Upgrading Coupled with Hydrogen Production under Industrial‐Level Current Density

Advanced Materials, Год журнала: 2023, Номер 35(25)

Опубликована: Март 25, 2023

As promising hydrogen energy carrier, formic acid (HCOOH) plays an indispensable role in building a complete industry chain of economy. Currently, the biomass upgrading assisted water electrolysis has emerged as attractive alternative for co-producing green HCOOH and H2 cost-effective manner, yet simultaneously affording high current density Faradaic efficiency (FE) still remains big challenge. Here, ternary NiVRu-layered double hydroxides (LDHs) nanosheet arrays selective glycerol oxidation evolution catalysis are reported, which yield industry-level 1 A cm-2 at voltage 1.933 V, meanwhile showing considerable productivities 12.5 17.9 mmol h-1 , with FEs almost 80% 96%, respectively. Experimental theoretical results reveal that introduced Ru atoms can tune local electronic structure Ni-based LDHs, not only optimizes adsorption kinetics HER, but also reduces reaction barriers both conversion NiII into GOR-active NiIII carboncarbon (CC) bond cleavage. In short, this work highlights potential large-scale productions from integrated electrocatalytic system provides new insights designing advanced electrocatalyst low-cost sustainable conversion.

Язык: Английский

---

Unraveling a bifunctional mechanism for methanol-to-formate electro-oxidation on nickel-based hydroxides

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Март 27, 2023

For nickel-based catalysts, in-situ formed nickel oxyhydroxide has been generally believed as the origin for anodic biomass electro-oxidations. However, rationally understanding catalytic mechanism still remains challenging. In this work, we demonstrate that NiMn hydroxide catalyst can enable methanol-to-formate electro-oxidation reaction (MOR) with a low cell-potential of 1.33/1.41 V at 10/100 mA cm-2, Faradaic efficiency nearly 100% and good durability in alkaline media, remarkably outperforming NiFe hydroxide. Based on combined experimental computational study, propose cyclic pathway consists reversible redox transitions NiII-(OH)2/NiIII-OOH concomitant MOR. More importantly, it is proved NiIII-OOH provides active sites including NiIII nearby electrophilic oxygen species, which work cooperative manner to promote either spontaneous or non-spontaneous MOR process. Such bifunctional well account not only highly selective formate formation but also transient presence NiIII-OOH. The different activities hydroxides be attributed their oxidation behaviors. Thus, our clear rational overall hydroxides, beneficial advanced design.

Язык: Английский

---

Recent Advancements in Electrochemical Hydrogen Production via Hybrid Water Splitting

Advanced Materials, Год журнала: 2023, Номер 36(4)

Опубликована: Окт. 10, 2023

Abstract As one of the most promising approaches to producing high‐purity hydrogen (H 2 ), electrochemical water splitting powered by renewable energy sources such as solar, wind, and hydroelectric power has attracted considerable interest over past decade. However, electrolysis process is seriously hampered sluggish electrode reaction kinetics, especially four‐electron oxygen evolution at anode side, which induces a high overpotential. Currently, emerging hybrid strategy proposed integrating thermodynamically favorable electro–oxidation reactions with cathode, providing new opportunity for energy–efficient H2 production. To achieve highly efficient cost–effective toward large–scale practical H production, much work been continuously done exploit alternative anodic oxidation cutting–edge electrocatalysts. This review will focus on recent developments production coupled reactions, including choice substrates, investigation electrocatalytic materials, deep understanding underlying mechanisms. Finally, some insights into scientific challenges now standing in way future advancement technique are shared, hope inspiring further innovative efforts this rapidly growing field.

Язык: Английский

---

Multi-heterointerfaces for selective and efficient urea production

National Science Review, Год журнала: 2022, Номер 10(2)

Опубликована: Окт. 4, 2022

ABSTRACT A major impediment to industrial urea synthesis is the lack of catalysts with high selectivity and activity, which inhibits efficient production urea. Here, we report a new catalyst system suitable for highly selective by in situ growth graphdiyne on surface cobalt–nickel mixed oxides. Such multi-heterojunction interfacial structure resulting obvious incomplete charge-transfer phenomenon between metal oxide interface multiple intermolecular interactions. These intrinsic characteristics are origin performance catalyst. Studies mechanism reveal that could effectively optimize adsorption/desorption capacities intermediate promote direct C–N coupling significantly suppressing by-product reactions toward formation H2, CO, N2 NH3. The can selectively synthesize directly from nitrite carbon dioxide water at room temperature pressure, exhibits record-high Faradaic efficiency 64.3%, nitrogen (Nurea-selectivity) 86.0%, (Curea-selectivity) ∼100%, as well yield rates 913.2 μg h−1 mgcat−1 remarkable long-term stability.

Язык: Английский

---

Recent Advances on Transition‐Metal‐Based Layered Double Hydroxides Nanosheets for Electrocatalytic Energy Conversion

Advanced Science, Год журнала: 2023, Номер 10(13)

Опубликована: Март 3, 2023

Abstract Transition‐metal‐based layered double hydroxides (TM‐LDHs) nanosheets are promising electrocatalysts in the renewable electrochemical energy conversion system, which regarded as alternatives to noble metal‐based materials. In this review, recent advances on effective and facile strategies rationally design TM‐LDHs electrocatalysts, such increasing number of active sties, improving utilization sites (atomic‐scale catalysts), modulating electron configurations, controlling lattice facets, summarized compared. Then, these fabricated for oxygen evolution reaction, hydrogen urea oxidation nitrogen reduction small molecule oxidations, biomass derivatives upgrading is articulated through systematically discussing corresponding fundamental principles reaction mechanism. Finally, existing challenges density catalytically future prospects nanosheets‐based each application also commented.

Язык: Английский

---

Scalable electrosynthesis of commodity chemicals from biomass by suppressing non-Faradaic transformations

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Сен. 12, 2023

Electrooxidation of biomass platforms provides a sustainable route to produce valuable oxygenates, but the practical implementation is hampered by severe carbon loss stemming from inherent instability substrates and/or intermediates in alkaline electrolyte, especially under high concentration. Herein, based on understanding non-Faradaic degradation, we develop single-pass continuous flow reactor (SPCFR) system with ratio electrode-area/electrolyte-volume, short duration time reactor, and separate feeding substrate solution, thus largely suppressing degradation. By constructing nine-stacked-modules SPCFR system, achieve electrooxidation glucose-to-formate 5-hydroxymethylfurfural (HMF)-to-2,5-furandicarboxylic acid (FDCA) conversion efficiency (SPCE; 81.8% 95.8%, respectively) selectivity (formate: 76.5%, FDCA: 96.9%) at concentrations 562.8 mM, 556.9 mM). Furthermore, demonstrate kilogram-scale electrosynthesis potassium diformate (0.7 kg) wood soybean oil, FDCA (1.17 HMF. This work highlights importance providing opportunities for scalable upgrading using electrochemical technology.

Язык: Английский

---

Renewable formate from sunlight, biomass and carbon dioxide in a photoelectrochemical cell

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Фев. 23, 2023

The sustainable production of chemicals and fuels from abundant solar energy renewable carbon sources provides a promising route to reduce climate-changing CO2 emissions our dependence on fossil resources. Here, we demonstrate solar-powered formate readily available biomass wastes feedstocks via photoelectrochemistry. Non-precious NiOOH/α-Fe2O3 Bi/GaN/Si wafer were used as photoanode photocathode, respectively. Concurrent photoanodic oxidation photocathodic reduction towards with high Faradaic efficiencies over 85% achieved at both photoelectrodes. integrated biomass-CO2 photoelectrolysis system reduces the cell voltage by 32% due thermodynamically favorable conventional water oxidation. Moreover, show solar-driven record-high yield 23.3 μmol cm-2 h-1 well robustness using hybrid photoelectrode system. present work opens opportunities for chemical fuel resources earth-sunlight, CO2.

Язык: Английский

---

The pivot to achieve high current density for biomass electrooxidation: Accelerating the reduction of Ni3+ to Ni2+

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 330, С. 122590 - 122590

Опубликована: Март 6, 2023

Язык: Английский

---

Double self-reinforced coordination modulation constructing stable Ni⁴⁺ for water oxidation

Energy & Environmental Science, Год журнала: 2024, Номер 17(4), С. 1468 - 1481

Опубликована: Янв. 1, 2024

Nitrate ligands and Co atoms not only promote the formation of Ni 4+ by accelerating deprotonation attracting electrons, but also adsorb electron-withdrawing bridge hydroxyl to stabilize .

Язык: Английский

---

Controllable Electron Distribution Reconstruction of Spinel NiCo₂O₄ Boosting Glycerol Oxidation at Elevated Current Density

Advanced Functional Materials, Год журнала: 2023, Номер 34(3)

Опубликована: Окт. 5, 2023

Abstract Electrocatalytic glycerol oxidation reaction (GOR) is an effective way to convert biomass byproduct high value‐added chemicals, which; however, suffers from the low activity and conversion ratio of presently available catalysts. Herein, NiCo 2 O 4 /NF bimetallic oxide nanoarray controllably fabricated by Ni substituting for octahedral Co 3+ in 3 , which exhibits excellent GOR catalytic at elevated current densities ( E 300 = 1.42 V, 600 1.62 V) overall Faradaic efficiency 97.5% V (FE formic acid 89.9% FE glycolic 7.62%). The performance attributed structure evolution including rapid generation III ‐OOH active species, optimized intermediates adsorption, accelerated electron transfer owing introduction, are evidenced operando spectroscopy measurements density functional theory calculations, respectively. GOR/hydrogen coupled two‐electrode electrolytic cell voltage ≈299 mV lower than that water splitting 50 mA cm −2 . More importantly, compared conventional splitting, this electrolyzer stable over 200 h 1.75 reducing energy consumption 16.9% obtaining products anode concurrently.

Язык: Английский

---