Reversible hydrogenation of carbon dioxide to formic acid using a Mn-pincer complex in the presence of lysine

Nature Energy, Год журнала: 2022, Номер 7(5), С. 438 - 447

Опубликована: Май 19, 2022

Abstract Efficient hydrogen storage and release are essential for effective use of as an energy carrier. In principle, formic acid could be used a convenient medium via reversible CO 2 hydrogenation. However, noble metal-based catalysts currently needed to facilitate the (de)hydrogenation, produced during is generally released, resulting in undesirable emissions. Here we report α -amino acid-promoted system hydrogenation using Mn-pincer complex homogeneous catalyst. We observe good stability reusability catalyst lysine amino at high productivities (CO hydrogenation: total turnover number 2,000,000; dehydrogenation: 600,000). Employing potassium lysinate, achieve >80% H evolution efficiency >99.9% retention ten charge–discharge cycles, avoiding re-loading steps between each cycle. This process was scaled up by factor 18 without obvious drop productivity.

Язык: Английский

---

Formic Acid to Power towards Low‐Carbon Economy

Advanced Energy Materials, Год журнала: 2022, Номер 12(15)

Опубликована: Фев. 23, 2022

Abstract The storage and utilization of low‐carbon electricity decarbonization transportation are essential components for the future energy transition into a economy. While hydrogen has been identified as potential carrier, lack viable technologies safe efficient H 2 greatly limits its applications deployment at scale. Formic acid (FA) is considered one promising carriers because high volumetric capacity 53 g /L, relatively low toxicity flammability convenient low‐cost transportation. FA can be employed to generate either in direct fuel cells (FCs) or indirectly an source FCs. enable large‐scale chemical eliminate energy‐intensive expensive processes liquefaction compression thus achieve higher efficiency broader utilization. This perspective summarizes recent advances catalyst development selective dehydrogenation high‐pressure production. advantages limitations FA‐to‐power options highlighted. Existing life cycle assessment (LCA) economic analysis studies reviewed discuss feasibility fuel.

Язык: Английский

---

Electroreduction of CO₂: Advances in the Continuous Production of Formic Acid and Formate

ACS Energy Letters, Год журнала: 2023, Номер 8(4), С. 1992 - 2024

Опубликована: Март 30, 2023

The study of the electrochemical CO2 reduction to obtain formate (HCOO–) or formic acid (HCOOH) is receiving much attention as a promising technology. Since continuous–mode operation has become necessary for practical implementation reduction, recent years have seen rapid increase in number research approaches focusing on this aspect. This Focus Review provides unified discussion available studies continuous electroreduction HCOO–/HCOOH, considering different important features process design. Moreover, paper quantitatively assesses performance that involve reactors converting HCOOH/HCOO–, comparing relevant typically used figures merit, including energy consumption. Although some trade-offs already been achieved, simultaneous optimization all merit remains challenge. Finally, concluding remarks highlight detected trends and discuss aspects will be tackled by future field.

Язык: Английский

---

Tunable Selectivity for Electrochemical CO₂ Reduction by Bimetallic Cu–Sn Catalysts: Elucidating the Roles of Cu and Sn

ACS Catalysis, Год журнала: 2021, Номер 11(17), С. 11103 - 11108

Опубликована: Авг. 20, 2021

Production of formate or CO from electrochemical CO2 reduction reactions (eCO2RRs) represents a promising way to utilize with future low-carbon electricity produce value-added chemicals and fuels. Herein, series Cu–Sn composite catalysts were designed for eCO2RRs. The products could be tuned selectively by varying the Cu/Sn composition. catalyst Cu1Sn1 CuSn alloy core SnO shell structure doped small amount Cu gives maximum faradic efficiency (FE) 95.4 at −1.2 V. In contrast, single-Sn-atom-doped Cu20Sn1 is selective FE 95.3% −1.0 DFT results reveal that existence amounts Sn single atoms in these two critical reducing reaction free energies reduction, resulting formation CO, respectively.

Язык: Английский

---

Continuous electroproduction of formate via CO2 reduction on local symmetry-broken single-atom catalysts

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

Опубликована: Окт. 27, 2023

Abstract Atomic-level coordination engineering is an efficient strategy for tuning the catalytic performance of single-atom catalysts (SACs). However, their rational design has so far been plagued by lack a universal correlation between symmetry and properties. Herein, we synthesised planar-symmetry-broken CuN 3 (PSB-CuN ) SACs through microwave heating electrocatalytic CO 2 reduction. Remarkably, as-prepared exhibited selectivity 94.3% towards formate at −0.73 V vs. RHE, surpassing symmetrical 4 catalyst (72.4% −0.93 RHE). In flow cell equipped with PSB-CuN electrode, over 90% was maintained average current density 94.4 mA cm −2 during 100 h operation. By combining definitive structural identification operando X-ray spectroscopy theoretical calculations, revealed that intrinsic local breaking from planar D configuration induces unconventional dsp hybridisation, thus strong activity microenvironment metal centre (i.e., number distortion), high preference production in moiety. The finding opens avenue designing specific symmetries selective electrocatalysis.

Язык: Английский

---

A Nanocomposite of Bismuth Clusters and Bi₂O₂CO₃ Sheets for Highly Efficient Electrocatalytic Reduction of CO₂ to Formate

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Окт. 29, 2022

The renewable-electricity-driven CO2 reduction to formic acid would contribute establishing a carbon-neutral society. current catalyst suffers from limited activity and stability under high selectivity the ambiguous nature of active sites. Herein, we report powerful Bi2 S3 -derived that demonstrates density 2.0 A cm-2 with formate Faradaic efficiency 93 % at -0.95 V versus reversible hydrogen electrode. energy conversion single-pass yield reach 80 67 %, respectively, durability reaches 100 h an industrial-relevant density. Pure concentration 3.5 mol L-1 has been produced continuously. Our operando spectroscopic theoretical studies reveal dynamic evolution into nanocomposite composed Bi0 clusters O2 CO3 nanosheets pivotal role -Bi2 interface in activation conversion.

Язык: Английский

---

Metal-organic framework derived dual-metal sites for electroreduction of carbon dioxide to HCOOH

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 311, С. 121377 - 121377

Опубликована: Апрель 7, 2022

Язык: Английский

---

Efficient Conversion of Biomass to Formic Acid Coupled with Low Energy Consumption Hydrogen Production from Water Electrolysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 26, 2023

The development of a new electrolytic water hydrogen production coupling system is the key to realize efficient and low-cost promote its practical application. Herein, green electrocatalytic biomass formic acid (FA) coupled has been developed. In such system, carbohydrates as glucose are oxidized FA using polyoxometalates (POMs) redox anolyte, while H2 evolved continuously at cathode. Among them, yield high 62.5 %, only liquid product. Furthermore, requires 1.22 V drive current density 50 mA cm-2 , Faraday efficiency close 100 %. Its electrical consumption 2.9 kWh Nm-3 (H2 ), which 69 % that traditional water. This work opens up promising direction for with conversion.

Язык: Английский

---

Recent advances of single-atom alloy catalyst: Properties, synthetic methods and electrocatalytic applications

Materials Today Catalysis, Год журнала: 2023, Номер 2, С. 100009 - 100009

Опубликована: Июнь 27, 2023

Developing high-performance and cost-effective electrocatalysts for clean renewable energy conversion process has been proved a promising approach to deal with the global environment issues. Single-atom alloy (SAA) catalyst, foreign metal atoms atomically dispersed in surface of host metal, combines merits conventional alloys single-atom catalysts. The maximum atomic utilization active unique structural electrical properties SAA offer great potential boosting electrocatalytic activity reducing cost manufacture. Meanwhile, well-defined sites raise an opportunity shed light on structure-activity relationship further direct synthesis high-efficiency electrocatalysts. Herein, we focus recent developments advanced catalysts discussed general SAAs. Then design principle synthetic methods were summarized. Next, highlighted practical applications SAAs chemicals production, including hydrogen evolution reaction, oxygen CO2 reduction N2 reaction other representative reactions. Finally, challenges future directions are presented.

Язык: Английский

---

Upcycling of non-biodegradable plastics by base metal photocatalysis

Chem, Год журнала: 2023, Номер 9(9), С. 2683 - 2700

Опубликована: Авг. 14, 2023

Язык: Английский

---