not available in supplied local text · Coordination Chemistry Reviews · 2024
Review of sulfur-modified metal-organic frameworks and MOF-derived catalysts for overall water splitting, with emphasis on HER/OER mechanisms, conductivity, electronic-structure modulation, mass transport, synthesis strategies and remaining scale-up challenges.
The review’s argument is preserved as a navigable set of section summaries.
Frames OWS as HER plus OER, motivates non-noble catalysts, and presents MOFs as porous, tunable but poorly conductive templates whose transport limits can be addressed by sulfur-containing materials.
Relevance: Core · p. 1 · Introduction
Covers complete sulfurisation/pyrolysis to porous TMSs, MESs and carbon-composite sulfides, with emphasis on narrow band gaps, d-band shifts, mesoporosity and morphology collapse risks.
Relevance: Core · p. 3 · Metal sulfides (MSs) derived from MOFs · Fig. 11; Table 6
Defines four general functionalisation routes: electronic/coordination modulation, self-sacrificial conversion, morphology/growth control and coupling to active or conductive components.
Relevance: Core · p. 2 · Modification methods of MOFs electrocatalysts · Fig. 5
Introduces MIL, ZIF and UiO families, argues that MOF derivatives outperform pristine MOFs, and identifies instability and finite intrinsic conductivity as persistent limits.
Relevance: Core · p. 2 · Typical MOFs and their derivatives for water splitting · Tables 2-3
Lists practical and mechanistic gaps: high-current stability, green synthesis, broader MOF precursor space, toxic sulfur sources, phase evolution, acidic activity and residual-ligand effects.
Relevance: Core · p. 4-5 · Outlook and challenges of sulfur-modified MOFs · Fig. 14
Reviews direct sulfur-ligand coordination, thiol/dithiolene SBUs, sulfur decoration and sulfur doping; highlights improved conductivity and intermediate binding but notes ligand oxidation and dopant-site control problems.
Relevance: Core · p. 2 · MOFs based on S-functionalized ligands (S-MOFs) · Tables 4-5; Figs. 7-10
Presents partial sulfurisation as a compromise between MOF topology and sulfide conductivity, emphasising heterointerfaces, charge redistribution, active oxyhydroxide reconstruction and CNT/carbon stabilisation.
Relevance: Core · p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs) · Figs. 12-13; Table 7
Defines sulfur modification as ligand incorporation, partial sulfide/MOF heterojunction formation, or full sulfide conversion, and explains sulfate/vacancy formation during alkaline OER.
Relevance: Core · p. 2 · Sulfur-modified MOFs for water splitting · Fig. 2; Fig. 6
Summarises HER Volmer, Heyrovsky and Tafel steps; OER AEM/LOM pathways; and the review's caution that dynamic catalyst evolution still needs study.
Relevance: Core · p. 1 · Basic mechanisms of water splitting · Table 1; Fig. 3; Fig. 4
Classification systems are attributed to this review and are not treated as a global material registry.
Figure 14 condenses the review's comparative judgement: conductivity and active-site benefits are balanced against reagent toxicity, leaching, poor pristine conductivity, aggregation and over-sulfurisation risks.
Categories: sulfur group-decorated MOFs using sulfur reagents · sulfur group-decorated MOFs by direct coordination · sulfur-doped MOFs · metal sulfides · sulfur-doped carbides · sulfides-embedded semi-MOFs
p. 10 · Outlook and challenges of sulfur-modified MOFs · Fig. 14
The review presents Tafel slopes at 298 K as a secondary diagnostic for assigning HER pathways.
Categories: Volmer (RDS)-Tafel · Volmer-Tafel (RDS) · Volmer (RDS)-Heyrovsky · Volmer-Heyrovsky (RDS)
p. 10 · Steps and mechanisms of HER · Table 1
Before focusing on sulfur, the review groups MOF modification around electronic, conversion, morphological and composite strategies.
Categories: surface electron configuration modulation · self-sacrificing template conversion · growth-condition and morphology control · coupling with active components or conductive carriers
p. 6 · Modification methods of MOFs electrocatalysts · Fig. 5
OER is organised around AEM using metal sites and LOM using lattice oxygen sites, while the review also cites newer dynamic pathways.
Categories: adsorbate evolution mechanism · lattice oxygen mechanism
p. 6 · Steps and mechanisms of OER · Fig. 4
The review explicitly distinguishes sulfur-containing ligands fixed in the coordination network from trace guest sulfur atoms that substitute or insert into the lattice.
Categories: sulfur group-decorated MOFs · sulfur-doped MOFs
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 9
The review's central classification separates sulfur as part of the coordination framework, sulfur as a route to full sulfide derivatives, and sulfur as a partial heterojunction-forming modification.
Categories: MOFs based on S-functionalized ligands · MOF-derived metal sulfides · metal sulfide-embedded semi-MOFs
p. 5 · Figures and tables · Fig. 2
Review-defined families retain their representative materials and conduction descriptions.
Common MOF scaffolds used as water-electrolysis catalyst precursors or templates, typically built from transition-metal nodes and carboxylate or imidazolate ligands.
Conduction: Pristine MOFs are generally limited by intrinsic poor conductivity, but their topology provides distributed mass/charge-transfer sites.
Representative materials: MIL-series MOFs · ZIFs · UiO-66
Nodes / linkers: Fe · Ni · Cr · Al · Co · Zn · Zr · dicarboxylic acids · imidazole-based ligands · 1,4-benzenedicarboxylate
p. 2 · Typical MOFs and their derivatives for water splitting · Tables 2-3
Porous sulfides obtained by sulfurising or calcining MOF precursors, including bimetallic sulfides, heterostructured sulfides, medium-entropy sulfides and carbon-composite sulfides.
Conduction: Narrower sulfide band gaps, higher DOS near the Fermi level, d-band shifts and carbon shells are used to rationalise better conductivity and intermediate adsorption.
Representative materials: NiCo2S4/CP · Fe1.2(CoNi)1.8S6 · Ni-Ni3S2@C · FeS2-MoS2@CoS2 · Fe@CoMo2S4/Ni3S2/NF
Nodes / linkers: Ni · Co · Fe · Mo · pyrolysed MOF ligands · N/O/P-containing precursor ligands
p. 3 · Metal sulfides (MSs) derived from MOFs · Fig. 11; Table 6
Partially sulfurised MOF materials retaining MOF topology while embedding metal sulfide clusters or nanoparticles to form heterogeneous electronic interfaces.
Conduction: Heterointerfaces redistribute charge, sulfide phases increase conductivity, and retained MOF porosity supports ion/electrolyte transport.
Representative materials: NiFe-MS/MOF@NF · Co@Ni/Fe-MS/MOF · Ni-M@C-130 · Co3S4/EC-MOF
Nodes / linkers: Ni · Fe · Co · MIL-type ligands · Ni-MOF nanosheet ligands · aromatic pi-conjugated ligands
p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs) · Figs. 12-13; Table 7
MOFs where trace sulfur atoms substitute for framework atoms or occupy interstitial sites without forming a new sulfur-group-decorated coordination polymer.
Conduction: Sulfur doping is said to reduce band gap, increase carrier concentration and redistribute charge near dopant sites.
Representative materials: S-NiFe(CN)5NO
Nodes / linkers: Ni · Fe · cyanide/nitrosyl-containing Ni/Fe MOF framework
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 10
MOFs in which sulfur is incorporated into the coordination framework as a metal-sulfur bond, heterocyclic sulfur, dithiolene motif or thiol functional group.
Conduction: Metal-sulfur and pi-conjugated dithiolene motifs are described as improving charge delocalisation and electron transport.
Representative materials: THTA-Co · S-Ni BDC · NiFe(DMBD)-MOF · HTT-Pb · UiO-67-(SH)2
Nodes / linkers: Co · Ni · NiFe · Pb · Zr · triphenylenehexathiol · DMBD · BDMT · dithiolene and thiol carboxylates
p. 2 · MOFs based on S-functionalized ligands (S-MOFs) · Table 5
Post-sulfurised MOFs where sulfur-containing groups are bonded into the framework, exemplified by sulfate-like Fe-O-S structures in Fe MOFs-SO3.
Conduction: The review emphasises new active centres and lower OER energy barriers rather than bulk conductivity alone.
Representative materials: Fe MOFs-SO3 · Fe-DMBD · S@Fe-BDC
Nodes / linkers: Fe · BDC-derived Fe MOF frameworks · sulfate/sulfonate-like groups
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 8; Fig. 9
Review-level synthesis principles remain separate from primary-study recipes.
Use carbon matrices or nanotubes to stabilise active sulfide/MOF components, provide conductive networks and improve electrolyte diffusion.
Claimed effects: Improves conductivity, mechanical strength, exposure of active centres and resistance to catalyst detachment.
Controlling variables: CNT incorporation · carbon matrix formation · nanoparticle encapsulation · porosity
Representative materials: Ni-M@C-130 · Ni-Ni3S2@C
Caveat: The review still treats detachment from conventional supports and over-pyrolysis as stability risks.
p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs) · Fig. 13
Integrate MOF catalysts with carbon cloth, carbon paper, nickel foam or copper foam to compensate for poor MOF conductivity and provide macroscopic current-collection pathways.
Claimed effects: Can improve electron transfer, but insulating binders and polymer films may block direct catalyst/electrolyte contact.
Controlling variables: substrate choice · binder use · mechanical adhesion · electrolyte contact
Representative materials: MOF/CC · MOF/CP · MOF/NF
Caveat: The review cautions that Nafion-like adhesives are almost insulating and may impair solvent access.
p. 2 · Modification methods of MOFs electrocatalysts · Fig. 5
Tune synthesis temperature, nucleation rate and solvent polarity to form high-surface-area morphologies that expose more sites and shorten mass/electron transport paths.
Claimed effects: Large specific surface area and ultrathin or hollow morphology increase exposed active sites and accelerate transport.
Controlling variables: temperature · nucleation rate · solvent polarity · nanocage or hollow morphology
Representative materials: ultrathin MOFs · hollow nanorods · nanocages · core-shell MOFs
Caveat: Morphology can be unstable during high-temperature sulfurisation or harsh annealing.
p. 2 · Modification methods of MOFs electrocatalysts · Fig. 5
Partially convert MOF regions into metal sulfides while retaining MOF topology and porosity, forming MS/MOF heterointerfaces.
Claimed effects: Combines periodic MOF topology with adjustable sulfide electronic structure and interface-induced charge redistribution.
Controlling variables: sulfurisation temperature · extent of conversion · sulfide phase · preserved MOF porosity
Representative materials: NiFe-MS/MOF@NF · Co@Ni/Fe-MS/MOF · Ni-M@C-130 · Co3S4/EC-MOF
Caveat: Dynamic evolution and actual catalytic origin remain unclear compared with the number of performance reports.
p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs) · Figs. 12-13
Expose a MOF precursor to sulfurisation reagents to introduce sulfur-containing groups without complete sulfide conversion.
Claimed effects: Can create new reactive active centres and couple thermocatalytic H trapping with OER electrocatalysis.
Controlling variables: sulfurisation reagent · reaction temperature · binding mode to metal node · extent of framework modification
Representative materials: Fe MOFs-SO3
Caveat: Mechanistic understanding of sulfur binding remains shallow, and sulfur reagents may be malodorous or toxic.
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 8
Introduce trace sulfur as a non-metal dopant that substitutes, inserts or partly leaches during alkaline OER to form vacancies and adsorbed sulfate.
Claimed effects: Charge redistribution, smaller band gap, higher carrier concentration and regulated intermediate adsorption.
Controlling variables: dopant concentration · doping site · alkaline leaching behaviour · vacancy anchoring
Representative materials: S-NiFe(CN)5NO
Caveat: Doping sites are difficult to control, so deliberately anchoring vacancies remains challenging.
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 10
Build sulfur into the MOF coordination framework through metal-sulfur links or sulfur-bearing organic ligands such as thiols and dithiolenes.
Claimed effects: Creates S-containing SBUs that modulate coordination environment, charge transfer and intermediate binding.
Controlling variables: metal-ligand coordination selectivity · ligand oxidation sensitivity · metal-soft base matching · framework symmetry
Representative materials: THTA-Co · S-Ni BDC · NiFe(DMBD)-MOF
Caveat: Thiol-containing ligands can be hard to store and transport because of oxidation susceptibility.
p. 2-3 · MOFs based on S-functionalized ligands (S-MOFs) · Table 5; Fig. 7
Use MOFs as templates or precursors that are partially or completely converted into conductive sulfides, phosphides, carbides or selenides.
Claimed effects: Improves catalytic properties and conductivity while potentially preserving templated porosity.
Controlling variables: sulfur source amount · annealing temperature · atmosphere · precursor morphology
Representative materials: NiCo2S4/CP · Fe1.2(CoNi)1.8S6 · Ni-Ni3S2@C
Caveat: Pyrolysis/annealing can shrink surface area, aggregate metals and collapse morphology.
p. 2 · Modification methods of MOFs electrocatalysts · Fig. 5
These are the review authors’ synthesis, not newly measured results.
The review acknowledges that dynamic catalyst evolution and actual OER reaction processes are not fully resolved, despite multiple proposed pathways beyond AEM and LOM.
Evidence basis: multi_reference
Caveat: Important for Chapter 1 because apparent catalyst identity can differ from the active reconstructed phase.
p. 1 · Steps and mechanisms of OER · Fig. 4
Fe MOFs-SO3 is interpreted as using SO3 groups as additional active centres that trap H in OER intermediates and cascade thermocatalysis with electrocatalysis to lower OER energy requirements.
Evidence basis: single_reference
Caveat: Single-study mechanism; useful as an example of coupled thermal/electrochemical interpretation rather than a settled general mechanism.
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 8
The review uses HER Tafel slope values as a secondary diagnostic for assigning Volmer/Tafel/Heyrovsky pathways and their rate-determining steps.
Evidence basis: review_reasoning
Caveat: Tafel interpretation is mechanism-guiding rather than definitive without complementary kinetic evidence.
p. 1 and p. 10 · Steps and mechanisms of HER · Table 1
The review argues that many reported catalysts are benchmarked only at 10 mA cm-2 and that conductivity and stability at ampere-level current densities are more relevant to industrial operation.
Evidence basis: review_reasoning
Caveat: This is a review-level outlook criterion for interpreting benchmark relevance.
p. 4-5 · Outlook and challenges of sulfur-modified MOFs · Fig. 14
MOFs offer large surface area, porosity, tunable nodes and accessible sites for charge/mass transport, but pristine MOFs remain constrained by water instability and poor intrinsic conductivity.
Evidence basis: multi_reference
Caveat: This is the review's synthesis of prior MOF electrocatalysis literature, not a new measurement.
p. 1-2 · Introduction; Typical MOFs and their derivatives
MOFs and TMSs are treated as pre-catalysts in alkaline OER because they can reconstruct in situ to metal oxyhydroxides, making post-reaction phase identification essential.
Evidence basis: multi_reference
Caveat: Review-level caution that nominal precursor composition may not equal active catalytic phase.
p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs) · Fig. 12
Sulfur doping is reviewed as a route to charge redistribution, smaller band gaps and higher carrier concentration, but the precise sulfur binding sites are difficult to control.
Evidence basis: multi_reference
Caveat: The review treats dopant-site control as a design bottleneck.
p. 3 · MOFs based on S-functionalized ligands (S-MOFs) · Figs. 9-10
Sulfur-functionalised ligands can act as SBUs that alter active-centre coordination and electron/intermediate capture, while pi-conjugated metal-dithiolene structures are described as favourable for charge transfer.
Evidence basis: multi_reference
Caveat: The review combines direct examples with general ligand-design arguments.
p. 2 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 7; Table 5
In alkaline OER, sulfur can oxidise before oxygen to generate sulfate and sulfur vacancies; the review interprets those vacancies and adsorbed sulfates as promoting reconstruction and OER activity.
Evidence basis: multi_reference
Caveat: Presented as a mechanistic rationale; active phase evolution still requires in situ verification for specific catalysts.
p. 2 · Sulfur-modified MOFs for water splitting · Fig. 6
Semi-MOF MS/MOF heterojunctions are presented as combining MOF periodic topology with sulfide electronic structure, where interfaces redistribute charge and reduce adsorption energies for OER/HER intermediates.
Evidence basis: multi_reference
Caveat: The review later notes that the origin of catalytic activity and dynamic evolution are still not comprehensively understood.
p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs)
Sulfur modification is presented as a way to activate MOF conductivity, accelerate multi-electron transfer and lower intermediate adsorption or reaction barriers in HER/OER.
Evidence basis: review_reasoning
Caveat: The claim is a broad review-level design rationale across multiple material classes.
p. 1 · Abstract · Fig. 1
For thiol-Ni frameworks, the review attributes improved OER/HER performance to stronger Ni-S covalency, enhanced charge delocalisation, metallic band structure and reduced intermediate energy barriers.
Evidence basis: multi_reference
Caveat: Mechanistic interpretation is drawn from cited experiments and DFT, not independently verified by the review.
p. 2 · MOFs based on S-functionalized ligands (S-MOFs) · Fig. 7
The review argues that MOF-derived transition-metal sulfides often show better conductivity than oxides due to narrower band gaps and sulphur-induced changes in DOS, d-band position and intermediate adsorption.
Evidence basis: multi_reference
Caveat: The review also states that few studies fully isolate how anion species affect OWS performance.
p. 3 · Metal sulfides (MSs) derived from MOFs · Fig. 11
Every row remains visibly secondary and links to a primary dossier only where the mapping is verified.
| Material | Property | Reported value | Context and quality | Primary evidence | Review source |
|---|---|---|---|---|---|
| SecondaryFe@CoMo2S4/Ni3S2/NF | OER overpotential at 10 mA cm-2 | eta10 = 167 mV; Tafel slope 13.77 mV dec-1; 100 h @ 10 mA cm-2; Fe doping | 1.0 M KOH for OER; secondary review Table 6 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 6 |
| SecondaryFe MOFs-SO3 | OER overpotential at 10 mA cm-2 | eta10 = 218 mV; eta500 = 298 mV; Tafel slope 36.2 mV dec-1; 1000 CVs; 1.0 M KOH | 1.0 M KOH for OER; secondary review Table 4 Table · Exact Reported | No verified corpus mapping | p. 11 · Figures and tables · Table 4 |
| SecondaryFeS2-MoS2@CoS2 | HER overpotential at 10 mA cm-2 | eta10 = 92 mV (HER); eta20 = 211 mV (OER); heterogeneous interface engineering | 1.0 M KOH for HER and OER; secondary review Table 6 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 6 |
| SecondaryFe1.2(CoNi)1.8S6 | OER overpotential series | 246, 277 and 289 mV at current densities of 10, 30 and 50 mA cm-2; 24 h at 10 mA cm-2 | Review text example of medium-entropy sulfide in alkaline OER Text · Exact Reported | No verified corpus mapping | p. 3 · Metal sulfides (MSs) derived from MOFs · Fig. 11 |
| SecondaryNi3S2/MIL-53(Fe) | HER overpotential at 10 mA cm-2 | eta10 = 214 mV; Tafel slope 33.8 mV dec-1; 24 h @ 0.1 A cm-2; 1.0 M KOH | 1.0 M KOH for HER; secondary review Table 7 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 7 |
| SecondaryNi-M@C-130 | HER overpotential at 10 mA cm-2 | eta10 = 123 mV (HER); Tafel slope 50.8 mV dec-1 (HER); 25 h; 1.0 M KOH | 1.0 M KOH for HER and OER; secondary review Table 7 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 7 |
| SecondaryNi-M@C-130 | OER overpotential at 10 mA cm-2 | eta10 = 244 mV (OER); Tafel slope 74.2 mV dec-1 (OER); 25 h; 1.0 M KOH | 1.0 M KOH for HER and OER; secondary review Table 7 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 7 |
| SecondaryN-doped Ni-Ni3S2@C | OER overpotential at 10 mA cm-2 | 284.7 mV at 10 mA cm-2 in alkaline solution | Alkaline OER; secondary review text Text · Exact Reported | No verified corpus mapping | p. 4 · Metal sulfides (MSs) derived from MOFs · Fig. 11 |
| SecondaryNiCo2S4/CP | HER overpotential at 10 mA cm-2 | eta10 = 87 mV (HER); Tafel slope 78.9 mV dec-1 (HER); 1.0 M KOH for HER and OER | 1.0 M KOH; secondary review Table 6 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 6 |
| SecondaryNiCo2S4/CP | OER overpotential at 25 mA cm-2 | eta25 = 251 mV (OER); Tafel slope 54.1 mV dec-1 (OER); 1.0 M KOH for HER and OER | 1.0 M KOH; secondary review Table 6 Table · Exact Reported | No verified corpus mapping | p. 12 · Figures and tables · Table 6 |
| SecondaryNiFe(DMBD)-MOF | OER overpotential at 50 mA cm-2 | eta50 = 263 mV; Tafel slope 54.3 mV dec-1; 24 h @ 250 mA cm-1; 1.0 M KOH | 1.0 M KOH for OER; secondary review Table 4 Table · Exact Reported | No verified corpus mapping | p. 11 · Figures and tables · Table 4 |
| SecondaryS-Ni BDC | HER overpotential at 1000 mA cm-2 | eta1000 = 310 mV; Tafel slope 75.0 mV dec-1; 150 h @ 1.0 A cm-2; 1.0 M KOH | 1.0 M KOH for HER; secondary review Table 4 Table · Exact Reported | No verified corpus mapping | p. 11 · Figures and tables · Table 4 |
| SecondaryS-NiFe(CN)5NO | OER overpotential at 10 mA cm-2 | eta10 = 274 mV; Tafel slope 54.4 mV dec-1; 1000 CVs; 1.0 M KOH | 1.0 M KOH for OER; secondary review Table 4 Table · Exact Reported | No verified corpus mapping | p. 11 · Figures and tables · Table 4 |
Open questions are presented as review-author priorities, not conclusions from the primary database.
Despite alkaline OER progress, TMS electrocatalytic activity in acidic media is described as limited.
Proposed direction: Use ligand engineering, heterostructure engineering and heteroatom doping to develop acid-suitable TMS HER/OER catalysts.
p. 5 · Outlook and challenges of sulfur-modified MOFs
MOF-derived HER/OER catalysts are said to rely heavily on ZIF-67 and familiar MOFs, leaving internal coordination environments and external synthesis conditions underexplored.
Proposed direction: Systematically vary MOF precursor metal/ligand environments, solvents, atmospheres and ionic species.
p. 4-5 · Outlook and challenges of sulfur-modified MOFs
Two-step pyrolysis is described as costly in time and economics, limiting commercialisation of existing catalysts.
Proposed direction: Develop low-cost, simple and environmentally benign sulfur-modification strategies.
p. 4 · Outlook and challenges of sulfur-modified MOFs
Most reviewed OER/HER reports focus on 10 mA cm-2, leaving conductivity and stability at >1 A cm-2 insufficiently examined.
Proposed direction: Prioritise ampere-level durability and transport measurements under industrially relevant current densities.
p. 4-5 · Outlook and challenges of sulfur-modified MOFs
The review states that OER mechanisms of MOFs and TMSs remain ambiguous.
Proposed direction: Apply mature theoretical modelling and calculation methods alongside experiments to clarify catalytic mechanisms.
p. 5 · Outlook and challenges of sulfur-modified MOFs
TMSs often reconstruct as oxyhydroxides, metals or hydroxides during OER/HER, so intermediates and phase evolution remain insufficiently resolved.
Proposed direction: Use in situ or operando characterisation to track active phases and intermediates under working conditions.
p. 5 · Outlook and challenges of sulfur-modified MOFs
The review notes that residual ligands after pyrolysis may promote catalytic activity, but their role requires more attention.
Proposed direction: Investigate how retained organic fragments influence conductivity, active sites and catalytic kinetics after MOF post-treatment.
p. 5 · Outlook and challenges of sulfur-modified MOFs
Sulfur dopant sites are difficult to control, making precise defect and vacancy anchoring a challenging design task.
Proposed direction: Develop structure-controlled doping strategies that locate sulfur atoms and vacancies at targeted binding positions.
p. 3 · MOFs based on S-functionalized ligands (S-MOFs)
For MS/MOF semi-MOFs, the review says dynamic evolution and the origin of catalytic activity remain incompletely understood.
Proposed direction: Pair interface-resolved structural studies with operando electrochemistry to separate MOF, sulfide and reconstructed-phase contributions.
p. 4 · Metal sulfides-embedded semi-MOFs (MSs/MOFs)
Heated thiourea, thioacetamide, Na2S and sulfur powder are described as malodorous, carcinogenic-risk and polluting sulfurisation agents.
Proposed direction: Promote in situ decomposition of sulfur-containing ligand-based MOFs to avoid additional sulfur sources.
p. 5 · Outlook and challenges of sulfur-modified MOFs
Mappings show which printed review references have a verified counterpart in the frozen primary corpus.
| Reference | Study | Role and context | Corpus mapping |
|---|---|---|---|
| Ref. 332022 | Title unavailable | transport_rationale · review_claimSupports the review claim that MOF surface area, internal cavities and topology aid charge/mass transport and active-site accessibility. | Unmapped |
| Ref. 342022 | Title unavailable | conductivity_limitation · review_claimCited for the review's statement that MOFs suffer poor conductivity associated with organic ligands. | Unmapped |
| Ref. 362022 | Title unavailable | oer_mechanism · review_claimCited for photon-induced coupled oxygen evolution and reversible NiOOH structural transformation. | Unmapped |
| Ref. 372022 | Title unavailable | oer_mechanism · review_claimCited for oxygen vacancy site mechanism involving reconfiguration of CoFe LDH on Cu2S. | Unmapped |
| Ref. 382022 | Title unavailable | oer_mechanism · review_claimCited for sequential oxidation kinetic mechanism and continuous cobalt valence changes in Co3O4. | Unmapped |
| Ref. 412020 | Title unavailable | semi_mof · synthesis_strategyCited as one-pot growth of FeNi-MIL ultrathin nanoplates implanted with Ni2S3 clusters on nickel foam. | Unmapped |
| Ref. 742022 | Title unavailable | sulfate_vacancy_mechanism · review_claimCited for the review's sulfate/vacancy rationale in alkaline OER. | Unmapped |
| Ref. 752023 | Title unavailable | sulfate_vacancy_mechanism · review_claimCited with Ref. 74 for sulfate adsorption/vacancy effects in alkaline OER. | Unmapped |
| Ref. 762019 | Title unavailable | s_functional_ligands · review_claimCited for sulfur-based ligand SBUs and sulfur as heteroatom dopant in MOFs. | Unmapped |
| Ref. 772018 | Title unavailable | s_functional_ligands · review_claimCited with Ref. 76 for MOF design using sulfur-based ligands as SBUs. | Unmapped |
| Ref. 782016 | Title unavailable | s_functional_ligands · mechanistic_exampleCited for single-layer Co-THTA MOF containing CoS2N2, CoS4 and CoN4 complexes and HER mechanism discussion. | Unmapped |
| Ref. 792022 | Title unavailable | secondary_benchmark · s_functional_ligands · herCited for S-decorated Ni-BDC nanosheet arrays and high-current alkaline HER activity. | Unmapped |
| Ref. 832020 | Title unavailable | electronic_structure · review_claimCited for p-band centre interpretation of thiol-decorated SNi BDC and enhanced electron transport capability. | Unmapped |
| Ref. 852023 | Title unavailable | secondary_benchmark · s_functional_ligands · oerCited for thiol-nickel NiFe(DMBD)-MOF nanosheets and OER performance/stability in alkaline media. | Unmapped |
| Ref. 882022 | Title unavailable | electronic_structure · review_claimCited for metallic band-structure and OER intermediate energy-barrier interpretation around NiS SBUs. | research_0892 |
| Ref. 892019 | Title unavailable | electronic_structure · review_claimCited with Ref. 88 for DFT/experimental interpretation of NiS SBU electronic effects. | Unmapped |
| Ref. 902023 | Title unavailable | secondary_benchmark · s_doped_mof · oerCited for sulfur-doped Ni/Fe-based MOF with improved electron conductivity and OER performance. | Unmapped |
| Ref. 922020 | Title unavailable | secondary_benchmark · post_sulfurization · oerCited for Fe MOFs-SO3, SO3 active centres and thermocatalytic cascade electrocatalysis in OER. | Unmapped |
| Ref. 932021 | Title unavailable | s_doping · review_claimCited for sulfur dopant substitution/interstitial behaviour and charge redistribution. | Unmapped |
| Ref. 962022 | Title unavailable | s_doping · review_claimCited in the review's discussion of sulfur dopants affecting band gaps and electronic conductivity. | Unmapped |
| Ref. 1042020 | Title unavailable | anion_doping · review_claimCited for the review's general statement that heterogeneous anions modulate metal-ion electronic configuration and intermediate adsorption/desorption. | Unmapped |
| Ref. 1052021 | Title unavailable | anion_doping · review_claimCited for the review's statement that S-doping changes the electronic microenvironment and generates vacancies with increased S. | Unmapped |
| Ref. 1192021 | Title unavailable | secondary_benchmark · mof_derived_sulfide · anion_effectCited for comparing sulfurised and oxidised NiCo-based MOF derivatives and for NiCo2S4/CP HER/OER table values. | Unmapped |
| Ref. 1202018 | Title unavailable | electronic_structure · review_claimCited for DOS/Fermi-level interpretation that sulfurisation makes NiCo2S4 more metallic than oxide analogue. | Unmapped |
| Ref. 1232019 | Title unavailable | d_band · review_claimCited for the d-band-centre interpretation of sulfurisation and intermediate adsorption. | Unmapped |
| Ref. 1242020 | Title unavailable | d_band · review_claimCited with Ref. 123 for d-band-centre effects and adsorption energy barriers. | Unmapped |
| Ref. 1272023 | Title unavailable | secondary_benchmark · medium_entropy_sulfideCited for MOF-derived medium-entropy sulfide nanoparticles and OER/ORR bifunctional performance. | Unmapped |
| Ref. 1382019 | Title unavailable | secondary_benchmark · carbon_composite_sulfideCited for Ni/Ni3S2 nanoparticles in N-doped carbon matrix using intrinsic sulfate source in a Ni-MOF. | Unmapped |
| Ref. 1422022 | Title unavailable | secondary_benchmark · mof_derived_sulfideCited in Table 6 as a heterogeneous-interface-engineered MOF-derived sulfide for HER/OER. | Unmapped |
| Ref. 1562023 | Title unavailable | secondary_benchmark · mof_derived_sulfideCited in Table 6 as a Fe-doped heterointerface sulfide OER catalyst. | Unmapped |
| Ref. 1682023 | Title unavailable | semi_mof_interface · review_claimCited for the review's claim that MS/MOF synergy can impair adsorption energies of OER/HER intermediates. | Unmapped |
| Ref. 1702020 | Title unavailable | precatalyst_reconstruction · review_claimCited for the claim that MOFs/TMSs can act as pre-catalysts and reconstruct during alkaline OER. | Unmapped |
| Ref. 1712020 | Title unavailable | precatalyst_reconstruction · semi_mof_interfaceCited both for alkaline OER reconstruction and for interface engineering context in semi-MOFs. | Unmapped |
| Ref. 1722018 | Title unavailable | precatalyst_reconstruction · review_claimCited for reconfiguration/phase evolution context during alkaline OER. | Unmapped |
| Ref. 1732018 | Title unavailable | precatalyst_reconstruction · review_claimCited with other reconstruction references for the pre-catalyst view of alkaline OER. | Unmapped |
| Ref. 1742020 | Title unavailable | precatalyst_reconstruction · review_claimCited with Refs. 170-173 for in-situ structural evolution during alkaline OER. | Unmapped |
| Ref. 1832024 | Title unavailable | semi_mof · synthesis_strategyCited for Co-doped, partially sulfurised NiFe-MIL with NiS2 embedding and alkaline self-reconstruction. | Unmapped |
| Ref. 1882021 | Title unavailable | secondary_benchmark · semi_mof · carbon_compositeCited for CNT-based semi-MOF Ni-M@C-130 and paired HER/OER benchmark values. | Unmapped |
| Ref. 1942019 | Title unavailable | semi_mof · synthesis_strategyCited for low-temperature surface sulfurisation of MOF with inherited hollow nanorod morphology. | Unmapped |
| Ref. 1962020 | Title unavailable | secondary_benchmark · semi_mofCited in Table 7 as a semi-MOF HER benchmark derived from MIL-53(Fe). | Unmapped |